Heteerocyclyl-substituted thiazoles as crop protection agents

ABSTRACT

Heterocyclyl-substituted thiazoles of the formula (I), 
     
       
         
         
             
             
         
       
     
     in which the symbols have the meanings given in the description, and also to the agrochemically active salts thereof, and their use for controlling phytopathogenic harmful fungi, and also processes for preparing compounds of the formula (I).

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to European Application 08165625.8filed Oct. 1, 2008, the content of which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Heterocyclyl-Substituted Thiazoles as Crop Protection Agents

The invention relates to heterocyclyl-substituted thiazoles and theiragrochemically active salts, to their use and to methods andcompositions for controlling phytopathogenic harmful fungi in and/or onplants or in and/or on seed of plants, to processes for preparing suchcompositions and treated seed and also to their use for controllingphytopathogenic harmful fungi in agriculture, horticulture and forestry,in animal husbandry, in the protection of materials and in the domesticand hygiene field. The present invention furthermore relates to aprocess for preparing heterocyclyl substituted thiazoles.

2. Description of Related Art

It is already known that certain heterocyclyl-substituted thiazoles canbe employed as fungicidal crop protection agents (see WO 07/014,290, WO08/013,925, WO 08/013,622, WO 08/091,594, WO 08/091,580, WO 09/055,514).However, the fungicidal activity of these compounds is, in particular atlow application rates, not always sufficient.

Since the ecological and economic demands made on modern crop protectionagents are increasing constantly, for example with respect to activityspectrum, toxicity, selectivity, application rate, formation of residuesand favourable manufacture, and there can furthermore be problems, forexample, with resistance, there is a constant need to develop novel cropprotection agents, in particular fungicides which, at least in someareas, have advantages over the known fungicides.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that the presentheterocyclyl-substituted thiazoles solve at least some aspects of theobjects mentioned and are suitable for use as crop protection agents, inparticular as fungicides.

Some heterocyclyl-substituted thiazoles are already known aspharmaceutically active compounds (see, for example, EP 1832586, WO04/058750, WO 04/058751, WO 05/003128, WO 06/032322, WO 07/104,558, WO07/115,805, WO 08/083,238), but not their surprising fungicidalactivity.

The invention provides compounds of the formula (I),

in which the symbols have the following meanings:

-   A represents methyl    or-   A represents unsubstituted or substituted phenyl,    where the substituents independently of one another are selected    from the list below    -   cyano, nitro, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl,        C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₄-C₁₀-cycloalkylalkyl,        C₄-C₁₀-alkylcycloalkyl, C₅-C₁₀-alkylcycloalkylalkyl,        C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl,        C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, benzyl, phenyl,        hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, OCH₂OCH₃, SH,        C₁-C₄-alkylthio, C₁-C₆-haloalkylthio, CHO, COOH,        (C₁-C₄-alkoxy)carbonyl, CONR⁶R⁷, CR⁶═NOR⁷,        (C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,        (C₁-C₄-alkyl)carbonyloxy, (C₁-C₄-alkyl)carbonylthio,        C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl,        C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphonyl, NR⁶R⁷, NR⁶COR⁷,        SF₅, SO₂NR⁶R⁷, C₂-C₄-alkoxyalkyl or 1-methoxycyclopropyl        or-   A is an optionally benzo-fused unsubstituted or substituted 5- or    6-membered heteroaryl, where the substituents independently of one    another are selected from the list below

Substituents at Carbon:

cyano, nitro, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,C₃-C₆-halocycloalkyl C₄-C₁₀-cycloalkylalkyl, C₄-C₁₀-alkylcycloalkyl,C₅-C₁₀-alkylcycloalkylalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, benzyl, phenyl,hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, OCH₂OCH₃, SH, C₁-C₄-alkylthio,C₁-C₆-haloalkylthio, CHO, COOH, (C₁-C₄-alkoxy)carbonyl, CONR⁶R⁷,CR⁶═NOR⁷, (C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,(C₁-C₄-alkyl)carbonyloxy, (C₁-C₄-alkyl)carbonylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylsulphonyl, NR⁶R⁷, NR⁶COR⁷, SF₅, SO₂NR⁶R⁷,C₂-C₄-alkoxyalkyl or 1-methoxycyclopropyl

Substituents at Nitrogen:

hydroxyl, NR⁶R⁷, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl, C₂-C₆-alkenyl,C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, or C₂-C₆-haloalkynyl

-   L¹ represents (C(R¹)₂)_(n)    where n=0 to 3-   R¹ are identical or different and independently of one another    represent hydrogen, halogen, C₁-C₂-alkyl, C₁-C₂-haloalkyl or cyano,    with the provision that L¹ may contain at most two R¹ different from    hydrogen-   Y represents sulphur or oxygen,-   W represents an unsubstituted or monosubstituted C₁- to C₃-carbon    chain, where the substituent is selected from the group consisting    of oxo, hydroxyl, cyano and C₁-C₄-alkyl-   X represents an unsubstituted or monosubstituted C₁- to C₂-carbon    chain, where the substituent is selected from the group consisting    of oxo, hydroxyl, cyano and C₁-C₄-alkyl-   R² represents hydrogen, C₁-C₂-alkyl, C₁-C₂-haloalkyl or halogen-   L² represents —C(R⁸)₂—C(R⁸)₂— or —CR⁹═CR⁹— or —C≡C—-   L³ represents a direct bond    or-   L³ represents a C₁- to C₄-carbon chain which may contain up to two    substituents, where the substituents independently of one another    are selected from the list below:    -   halogen, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-haloalkyl or        C₃-C₆-cycloalkyl-   R³ represents methyl, C₁-C₂-haloalkyl, —CH═CH₂, —C≡CH, or    unsubstituted or monosubstituted C₃-C₁₀-cycloalkyl, where the    substituent is selected from the list below:    -   cyano, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,        C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl,        C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, phenyl, hydroxyl, oxo,        C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyloxy,        C₂-C₆-alkynyloxy, C₁-C₆-alkylthio or C₁-C₆-haloalkylthio,        or-   R³ represents unsubstituted or substituted phenyl,    where the substituents independently of one another are selected    from the list below:    -   cyano, nitro, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl,        C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₄-C₁₀-cycloalkylalkyl,        C₄-C₁₀-halocycloalkylalkyl, C₄-C₁₀-alkylcycloalkyl,        C₅-C₁₀-alkylcycloalkylalkyl, C₄-C₁₀-cycloalkoxyalkyl,        C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₃-C₈-cycloalkenyl,        C₃-C₈-halocycloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl,        C₂-C₆-alkoxyalkyl, C₂-C₆-haloalkoxyalkyl,        C₃-C₈-alkoxyalkoxyalkyl, tri(C₁-C₂-alkyl)silyl, benzyl, phenyl,        hydroxyl, C₁-C₆-alkoxy, C₂-C₆-alkoxyalkoxy, C₁-C₆-haloalkoxy,        C₂-C₆-alkenyloxy, C₂-C₆-haloalkenyloxy, C₂-C₆-alkynyloxy,        C₂-C₆-haloalkynyloxy, C₃-C₆-cycloalkoxy, C₃-C₆-cycloalkyloxy,        C₃-C₆-halocycloalkoxy, C₄-C₁₀-cycloalkylalkyloxy, NR⁶R⁷, SH,        SF₅, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₂-C₆-alkylalkylthio,        C₃-C₆-cycloalkylthio, CHO, COOH, (C₁-C₆-alkoxy)carbonyl,        CONR⁶R⁷, CR⁶═NOR⁷, (C₁-C₆-alkyl)carbonyl,        (C₁-C₆-haloalkyl)carbonyl, (C₁-C₆-alkyl)carbonyloxy,        (C₁-C₆-haloalkyl)carbonyloxy, (C₁-C₆-alkyl)carbonylthio,        C₁-C₆-alkylsulphinyl, C₁-C₆-haloalkylsulphinyl,        C₁-C₆-alkylsulphonyl, C₁-C₆-haloalkylsulphonyl, NR⁶COR⁷ or        SO₂NR⁶R⁷        or-   R³ represents saturated or partially or fully unsaturated naphthyl    or indenyl    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    -   cyano, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,        C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl,        C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, phenyl, hydroxyl,        C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyloxy,        C₂-C₆-alkynyloxy, C₁-C₆-alkylthio or C₁-C₆-haloalkylthio,        or-   R³ represents an unsubstituted or substituted 5- or 6-membered    heteroaryl radical,    where the substituents independently of one another are selected    from the list below:    substituents at carbon: cyano, nitro, halogen, C₁-C₆-alkyl,    C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl    C₄-C₁₀-cycloalkylalkyl, C₄-C₁₀-alkylcycloalkyl,    C₅-C₁₀-alkylcycloalkylalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,    C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, benzyl,    phenyl, hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, OCH₂OCH₃, SH,    C₁-C₄-alkylthio, C₁-C₆-haloalkylthio, COOH, (C₁-C₄-alkoxy)carbonyl,    CONR⁶R⁷, (C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,    (C₁-C₄-alkyl)carbonyloxy, (C₁-C₄-alkyl)carbonylthio,    C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl,    C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphonyl, NR⁶R⁷, NR⁶COR⁷, SF₅,    SO₂NR⁶R⁷, C₂-C₄-alkoxyalkyl or 1-methoxycyclopropyl    substituents at nitrogen: hydroxyl, C₁-C₆-alkyl, C₁-C₃-haloalkyl,    C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl,    C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl    or phenyl    or-   R³ represents benzo-fused unsubstituted or substituted 5- or    6-membered heteroaryl which may contain up to two substituents,    where the substituents independently of one another are selected    from the list below:    substituents at carbon: cyano, nitro, halogen, C₁-C₆-alkyl,    C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl    C₄-C₁₀-cycloalkylalkyl, C₄-C₁₀-alkylcycloalkyl,    C₅-C₁₀-alkylcycloalkylalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,    C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, benzyl,    phenyl, hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, OCH₂OCH₃, SH,    C₁-C₄-alkylthio, C₁-C₆-haloalkylthio, COOH, (C₁-C₄-alkoxy)carbonyl,    CONR⁶R⁷, (C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,    (C₁-C₄-alkyl)carbonyloxy, (C₁-C₄-alkyl)carbonylthio,    C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl,    C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphonyl, NR⁶R⁷, NR⁶COR⁷, SF₅,    SO₂NR⁶R⁷, C₂-C₄-alkoxyalkyl or 1-methoxycyclopropyl    substituents at nitrogen: C₁-C₆-alkyl, C₁-C₃-haloalkyl,    C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl,    C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl    or phenyl    or-   R³ is an unsubstituted or monosubstituted 5- to 15-membered    heterocyclyl radical which is attached via a carbon atom and which    may contain up to two further heteroatoms selected from the group    consisting of nitrogen, oxygen and sulphur, where the substituent is    selected from the list below:    substituents at carbon: cyano, halogen, C₁-C₆-alkyl,    C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,    C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, phenyl,    hydroxyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyloxy,    C₂-C₆-alkynyloxy, C₁-C₆-alkylthio or C₁-C₆-haloalkylthio    substituents at nitrogen: C₁-C₆-alkyl, C₁-C₃-haloalkyl,    C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl,    C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl or phenyl-   R⁶, R⁷ independently of one another represent hydrogen, C₁-C₄-alkyl,    C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,-   R⁸ are identical or different and independently of one another    represent hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,    C₃-C₆-cycloalkyl or C₁-C₃-haloalkyl,-   R⁹ are identical or different and independently of one another    represent hydrogen, C₁-C₄-alkyl, or C₃-C₆-cycloalkyl,    and also agrochemically active salts thereof.

The invention also provides the use of the compounds of the formula (I)as fungicides.

DETAILED DESCRIPTION

Heterocyclyl-substituted thiazoles of the formula (I) according to theinvention and also their agrochemically active salts are highly suitablefor controlling phytopathogenic harmful fungi. The compounds accordingto the invention mentioned above have in particular strong fungicidalactivity and can be used both in crop protection, in the domestic andhygiene field and in the protection of materials.

The compounds of the formula (I) can be present both in pure form and asmixtures of various possible isomeric forms, in particular ofstereoisomers, such as E and Z, threo and erythro, and also opticalisomers, such as R and S isomers or atropisomers, and, if appropriate,also of tautomers. What is claimed are both the E and the Z isomers, andthe threo and erythro, and also the optical isomers, mixtures of theseisomers, and also the possible tautomeric forms.

Preference is given to compounds of the formula (I) in which one or moreof the symbols have one of the meanings below:

-   A represents methyl    or-   A represents phenyl which may contain up to two substituents, where    the substituents independently of one another are selected from the    list below:    -   cyano, nitro, halogen, C₁-C₄-alkyl, C₁-C₃-haloalkyl,        C₃-C₆-cycloalkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, hydroxyl,        C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,        C₁-C₄-haloalkylthio, (C₁-C₄-alkoxy)carbonyl,        (C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,        C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl,        C₁-C₄-alkylsulphonyl or C₁-C₄-haloalkylsulphonyl,        or-   A represents a heteroaromatic radical selected from the group below:    furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl,    isoxazol-4-yl, isoxazol-5-yl, 1H-pyrrol-1-yl, 1H-pyrrol-2-yl,    1H-pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl,    thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl,    isothiazol-5-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl,    imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, 1,2,4-oxadiazol-3-yl,    1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl,    1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl,    1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl,    1,2,4-triazol-3-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl,    pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl,    pyrimidin-5-yl, pyrazin-2-yl, 1,3,5-triazin-2-yl,    1,2,4-triazin-3-yl, 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl,    1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl,    1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl,    benzimidazol-5-yl, 1H-indazol-1-yl, 1H-indazol-3-yl,    1H-indazol-4-yl, 1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl,    2H-indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl,    1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl,    1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl,    1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl,    1-benzothiophen-7-yl, 1,3-benzothiazol-2-yl, 1,3-benzoxazol-2-yl,    quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl,    quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl,    isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl,    isoquinolin-6-yl, isoquinolin-7-yl or isoquinolin-8-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    substituents at carbon: cyano, halogen, C₁-C₄-alkyl,    C₁-C₃-haloalkyl, hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,    C₁-C₄-alkylthio or C₁-C₄-haloalkylthio,    substituents at nitrogen: C₁-C₄-alkyl, C₁-C₃-haloalkyl, cyclopropyl,    C₂-C₄-alkenyl or C₂-C₄-alkynyl,-   L¹ represents (C(R¹)₂)_(n)    where n=0 to 3-   R¹ are identical or different and independently of one another    represent hydrogen, chlorine, fluorine, methyl, CF₃ or cyano,    with the provision that L¹ may contain at most two R¹ different from    hydrogen,-   Y represents sulphur or oxygen,-   W represents an unsubstituted or monosubstituted C₁- to C₂-carbon    chain, where the substituent is selected from the group consisting    of cyano and C₁-C₂-alkyl,-   X represents an unsubstituted or monosubstituted C₁- to C₂-carbon    chain, where the substituent is selected from the group consisting    of cyano and C₁-C₂-alkyl,-   R² represents hydrogen, C₁-C₂-alkyl or halogen,-   L² represents —C(R⁸)₂—C(R⁸)₂— or —CR⁹═CR⁹— or —C≡C—,-   L³ represents a direct bond,    or-   L³ represents a C₁- to C₄-carbon chain which may contain up to two    substituents, where the substituents independently of one another    are selected from the list below:    -   C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-haloalkyl or cyclopropyl,-   R³ represents methyl, C₁-C₂-haloalkyl, —CH═CH₂, —C≡CH, or    unsubstituted or monosubstituted C₃-C₁₀-cycloalkyl, where the    substituent is selected from the list below:    -   halogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl,        C₂-C₆-alkynyl, tri(C₁-C₂-alkyl)silyl, phenyl or oxo,        or-   R³ represents phenyl which may contain up to three substituents,    where the substituents independently of one another are selected    from the list below:    -   cyano, nitro, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl,        C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₂-C₆-alkenyl,        C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl,        tri(C₁-C₂-alkyl)silyl, phenyl, hydroxyl, C₁-C₆-alkoxy,        C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-haloalkylthio,        or-   R³ represents naphthalen-1-yl, naphthalen-2-yl,    1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,    1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,    1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl,    2,3-dihydro-1H-inden-1-yl, 2,3-dihydro-1H-inden-2-yl,    2,3-dihydro-1H-inden-4-yl or 2,3-dihydro-1H-inden-5-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    cyano, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,    phenyl, hydroxyl, C₁-C₆-alkoxy, C₁-C₃-haloalkoxy, C₁-C₆-alkylthio or    C₁-C₃-haloalkylthio,    or-   R³ represents furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl,    isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1H-pyrrol-1-yl,    1H-pyrrol-2-yl, 1H-pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl,    oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,    isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,    pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,    imidazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,    1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,    1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl,    1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl,    pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl,    pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl,    pyrazin-2-yl, 1,3,5-triazin-2-yl or 1,2,4-triazin-3-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    substituents at carbon: cyano, halogen, C₁-C₆-alkyl,    C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, phenyl, hydroxyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio,    substituents at nitrogen: C₁-C₆-alkyl, C₁-C₃-haloalkyl,    C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or phenyl,    or-   R³ represents 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl,    1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl,    1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl,    benzimidazol-5-yl, 1H-indazol-1-yl, 1H-indazol-3-yl,    1H-indazol-4-yl, 1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl,    2H-indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl,    1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl,    1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl,    1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl,    1-benzothiophen-7-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl,    quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl,    isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl,    isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl or    isoquinolin-8-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    substituents at carbon: cyano, halogen, C₁-C₆-alkyl,    C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, phenyl, hydroxyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio,    substituents at nitrogen: C₁-C₆-alkyl, C₁-C₃-haloalkyl,    C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or phenyl,    or-   R³ represents an unsubstituted or monosubstituted 5- to 6-membered    heterocyclyl radical which is attached via a carbon atom and which    may contain up to two further heteroatoms selected from the group    consisting of nitrogen, oxygen and sulphur, where the substituent is    selected from the list below:    substituents at carbon: C₁-C₆-alkyl, C₁-C₃-haloalkyl,    C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,    tri(C₁-C₂-alkyl)silyl or phenyl,    substituents at nitrogen: C₁-C₆-alkyl, C₃-C₆-cycloalkyl,    C₂-C₆-alkenyl, C₂-C₆-alkynyl, tri(C₁-C₂-alkyl)silyl or phenyl,-   R⁸ are identical or different and independently of one another    represent hydrogen, halogen, C₁-C₂-alkyl, C₁-C₂-alkoxy, cyclopropyl    or C₁-C₂-haloalkyl,-   R⁹ are identical or different and independently of one another    represent hydrogen, C₁-C₂-alkyl, or cyclopropyl    and also to the agrochemically active salts thereof.

Particular preference is given to compounds of the formula (I) in whichone or more of the symbols have one of the meanings below:

-   A represents methyl,    or-   A represents phenyl which may contain up to two substituents, where    the substituents independently of one another are selected from the    list below:    -   cyano, nitro, halogen, C₁-C₂-alkyl, C₁-C₂-haloalkyl, hydroxyl,        C₁-C₂-alkoxy or C₁-C₂-haloalkoxy,        or-   A represents a heteroaromatic radical selected from the group below:    furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, oxazol-2-yl,    oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl;    pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl,    imidazol-2-yl, imidazol-4-yl, 1,2,4-triazol-1-yl, pyridin-2-yl,    pyridin-3-yl, pyridin-4-yl, 1,2,4-triazin-3-yl, 1H-benzimidazol-2-yl    or 1,3-benzothiazol-2-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    substituents at carbon: cyano, halogen, C₁-C₂-alkyl,    C₁-C₂-haloalkyl, hydroxyl, C₁-C₂-alkoxy or C₁-C₂-haloalkoxy,    substituents at nitrogen: C₁-C₂-alkyl or C₁-C₂-haloalkyl,-   L¹ represents (C(R¹)₂)_(n)    where n=0 to 3,-   R¹ are identical or different and independently of one another    represent hydrogen or methyl,    with the provision that L¹ may contain at most two methyl    substituents,-   Y represents sulphur or oxygen,-   W represents —CH₂CH₂—,-   X represents —CH₂CH₂—,-   R² represents hydrogen, methyl or halogen,-   L² represents —C(R⁸)₂—C(R⁸)₂— or —CR⁹═CR⁹— or —C≡C—,-   L³ represents a direct bond,    or-   L³ represents a C₁- to C₄-carbon chain which may contain up to two    substituents, where the substituents independently of one another    are selected from the list below:    -   methyl, methoxy or CF₃,-   R³ represents methyl, C₁-C₂-haloalkyl, —CH═CH₂, —C≡CH, or    unsubstituted or monosubstituted C₃-C₁₀-cycloalkyl, where the    substituent is selected from the list below:    -   fluorine, chlorine, methyl, ethyl, cyclopropyl, cyclopentyl or        cyclohexyl,        or-   R³ represents phenyl which may contain up to three substituents,    where the substituents independently of one another are selected    from the list below:    -   cyano, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, phenyl, hydroxyl,        C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or        C₁-C₆-haloalkylthio,        or-   R³ represents naphthalen-1-yl, naphthalen-2-yl,    1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,    1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,    1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl,    2,3-dihydro-1H-inden-1-yl, 2,3-dihydro-1H-inden-2-yl,    2,3-dihydro-1H-inden-4-yl or 2,3-dihydro-1H-inden-5-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    fluorine, chlorine, bromine, iodine, methyl, ethyl, CF₃, CHF₂,    cyclopropyl, phenyl, hydroxyl, OMe, OEt, OCF₃, OCHF₂, OC₂F₅, SMe or    SCF₃,    or-   R³ represents furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl,    isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1H-pyrrol-1-yl,    1H-pyrrol-2-yl, 1H-pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl,    oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,    isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,    pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,    imidazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,    1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,    1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl,    1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl,    pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl,    pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl,    pyrazin-2-yl, 1,3,5-triazin-2-yl or 1,2,4-triazin-3-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    -   substituents at carbon: cyano, fluorine, chlorine, bromine,        iodine, methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, CF₃,        CHF₂, C₂F₅, CCl₃, cyclopropyl, phenyl, hydroxyl, OMe, OEt,        OisoPr, OCF₃, OCHF₂, OC₂F₅, SMe or SCF₃,    -   substituents at nitrogen: methyl, ethyl, 1-methylethyl,        1,1-dimethylethyl, cyclopropyl or phenyl,        or-   R³ represents 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl,    1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl,    1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl,    benzimidazol-5-yl, 1H-indazol-1-yl, 1H-indazol-3-yl,    1H-indazol-4-yl, 1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl,    2H-indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl,    1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl,    1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl,    1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl,    1-benzothiophen-7-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl,    quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl,    isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl,    isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl or    isoquinolin-8-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    -   substituents at carbon: cyano, fluorine, chlorine, bromine,        iodine, methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, CF₃,        CHF₂, C₂F₅, CCl₃, cyclopropyl, phenyl, hydroxyl, OMe, OEt,        OisoPr, OCF₃, OCHF₂, OC₂F₅, SMe or SCF₃,    -   substituents at nitrogen: methyl, ethyl, 1-methylethyl,        1,1-dimethylethyl, cyclopropyl or phenyl,        or-   R³ represents unsubstituted or monosubstituted pyrrolidin-2-yl,    pyrrolidin-3-yl, morpholin-3-yl, morpholin-2-yl, piperidin-2-yl,    piperidin-3-yl or piperazin-2-yl, where the substituent is selected    from the list below:    -   substituents at carbon: methyl, ethyl, CF₃, cyclopropyl or        phenyl,    -   substituents at nitrogen: methyl, ethyl, cyclopropyl or phenyl,-   R⁸ are identical or different and independently of one another    represent hydrogen, methyl, ethyl or CF₃,-   R⁹ are identical or different and independently of one another    represent hydrogen, methyl or ethyl,    and also to the agrochemically active salts thereof.

Very particular preference is given to compounds of the formula (I) inwhich one or more of the symbols have one of the meanings below:

-   A represents methyl,    or-   A represents phenyl which may contain up to two substituents, where    the substituents independently of one another are selected from the    list below: cyano, fluorine, chlorine, bromine, iodine, methyl,    ethyl, CF₃, CHF₂, C₂F₅, CCl₃, hydroxyl, OMe, OCF₃, OCHF₂, OCH₂CF₃ or    OC₂F₅,    or-   A represents a heteroaromatic radical selected from the group below:    thiophen-3-yl, pyrazol-1-yl, pyrazol-4-yl, pyridin-4-yl,    1H-benzimidazol-2-yl or 1,3-benzothiazol-2-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    -   substituents at carbon: cyano, fluorine, chlorine, bromine,        iodine, methyl, ethyl, CF₃, CHF₂, C₂F₅, CCl₃, hydroxyl, OMe,        OCF₃, OCHF₂, OCH₂CF₃ or OC₂F₅,    -   substituents at nitrogen: methyl, ethyl or CF₃,-   L¹ represents (C(R¹)₂)_(n)    where n=0 to 3,-   R¹ are identical or different and independently of one another    represent hydrogen or methyl, with the provision that L¹ may contain    at most one methyl substituent,-   Y represents sulphur or oxygen,-   W represents —CH₂CH₂—,-   X represents —CH₂CH₂—,-   R² represents hydrogen, methyl, chlorine or bromine,-   L² represents —C(R⁸)₂—C(R⁸)₂— or —CR⁹═CR⁹— or —C≡C—,-   L³ represents a direct bond,    or-   L³ represents a C₁- to C₄-carbon chain,-   R³ represents methyl, CF₃, —CH═CH₂, —C≡CH, cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl,    or-   R³ represents phenyl which may contain up to two substituents, where    the substituents independently of one another are selected from the    list below:    -   cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl,        1-methylethyl, 1,1-dimethylethyl, CF₃, CHF₂, C₂F₅, CCl₃, phenyl,        hydroxyl, OMe, OEt, OisoPr, OCF₃, OCHF₂, OC₂F₅, SMe or SCF₃,        or-   R³ represents naphthalen-1-yl, naphthalen-2-yl,    1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,    1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,    1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl,    2,3-dihydro-1H-inden-1-yl, 2,3-dihydro-1H-inden-2-yl,    2,3-dihydro-1H-inden-4-yl or 2,3-dihydro-1H-inden-5-yl,    or-   R³ represents furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl,    isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1H-pyrrol-1-yl,    1H-pyrrol-2-yl, 1H-pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl,    oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,    isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,    pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,    imidazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,    1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,    1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl,    1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl,    pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl,    pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl,    pyrazin-2-yl, 1,3,5-triazin-2-yl or 1,2,4-triazin-3-yl,    or-   R³ represents 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl,    1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl,    1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl,    benzimidazol-5-yl, 1H-indazol-1-yl, 1H-indazol-3-yl,    1H-indazol-4-yl, 1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl,    2H-indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl,    1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl,    1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl,    1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl,    1-benzothiophen-7-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl,    quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl,    isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl,    isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl or    isoquinolin-8-yl,    or-   R³ represents pyrrolidin-2-yl, pyrrolidin-3-yl, morpholin-3-yl,    morpholin-2-yl, piperidin-2-yl, piperidin-3-yl or piperazin-2-yl,-   R⁸ are identical or different and independently of one another    represent hydrogen, methyl or ethyl,-   R⁹ are identical or different and independently of one another    represent hydrogen, methyl or ethyl,    and also to the agrochemically active salts thereof.

Extraordinary preference is given to compounds of the formula (I) inwhich one or more of the symbols have one of the meanings below:

-   A represents methyl, 1,3-dihydro-2H-indazol-2-yl, 3-chlorophenyl,    2,5-dichlorophenyl, 3-(trifluoromethyl)phenyl, 3,4-dimethoxyphenyl,    2,5-dibromophenyl, 2-bromo-5-(trifluoromethyl)phenyl,    5-bromo-2-methylphenyl, 5-iodo-2-methylphenyl,    2,5-bis(trifluoromethyl)phenyl, 2-chloro-5-(trifluoromethyl)phenyl,    1H-pyrazol-1-yl, 3-(trifluoromethyl)-1H-pyrazol-1-yl,    3,5-dimethyl-1H-pyrazol-1-yl,    5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl,    4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl,    3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl,    5-(difluoromethyl)-3-methyl-1H-pyrazol-1-yl,    3,5-dichloro-1H-pyrazol-1-yl, 3,5-dibromo-1H-pyrazol-1-yl,    5-chloro-1-methyl-1H-pyrazol-4-yl, thiophen-3-yl, pyridin-4-yl,    3-chloro-5-(trifluoromethyl)pyridin-2-yl, 1H-benzimidazol-2-yl or    1,3-benzothiazol-2-yl,-   L¹ is a direct bond,    or-   L¹ represents —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂— or —CHCH₃—,-   Y represents sulphur or oxygen,-   W represents —CH₂CH₂—,-   X represents —CH₂CH₂—,-   R² represents hydrogen, methyl or bromine,-   L² represents —CH₂CH₂—, —CH₂CHCH₃—, —CH═CH— (Z), —CH═CH— (E) or    —C≡C—,-   L³ represents a direct bond,    or-   L³ represents —CH₂—, —CH₂C(CH₃)₂—, —CH₂CHCH₃—,-   R³ represents methyl, —CH═CH₂, —C≡CH, CF₃, cyclohexyl, phenyl,    4-chlorophenyl, 4-methoxyphenyl, 3-(trifluoromethyl)phenyl,    naphthalen-1-yl, naphthalen-2-yl or pyridin-3-yl, and also to the    agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   A represents unsubstituted or substituted pyrazol-1-yl or    pyrazol-4-yl,    which may contain up to two substituents, where the substituents    independently of one another are selected from the list below:    -   substituents at carbon: cyano, fluorine, chlorine, bromine,        iodine, methyl, ethyl, CF₃, CHF₂, C₂F₅, CCl₃, hydroxyl, OMe,        OCF₃, OCHF₂, OCH₂CF₃, or OC₂F₅,    -   substituents at nitrogen: methyl, ethyl or CF₃,        and L₁ represents —CH₂—,        where the other substituents have one or more of the meanings        mentioned above,        and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   A represents unsubstituted or substituted phenyl,    where the substituents independently of one another are selected    from the list below:    cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, CF₃,    CHF₂, C₂F₅, CCl₃, hydroxyl, OMe, OCF₃, OCHF₂, OCH₂CF₃ or OC₂F₅,    and L¹ represents —CH₂—,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   Y represents oxygen,    where the other substituents have one or more of the meanings    mentioned above, and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which one or more of the symbols have one of the meaningsbelow:

-   W represents —CH₂CH₂—-   X represents —CH₂CH₂—    where the other substituents have one or more of the meanings    mentioned above, and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   R² represents hydrogen, halogen or methyl,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   L² represents —CH₂CH₂—,    where the other substituents have one or more of the meanings    mentioned above, and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   L² represents —CH═CH— (Z),    where the other substituents have one or more of the meanings    mentioned above, and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   L² represents —CH═CH— (E),    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   L² represents —C≡C—,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   L³ represents a direct bond,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   L³ represents —CH₂—,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   R³ represents unsubstituted naphthalen-1-yl or naphthalen-2-yl,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   R³ represents unsubstituted phenyl,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   A represents 2,5-dimethylphenyl, 2,3,6-trifluorophenyl,    3,5-bis(difluoromethyl)-1H-pyrazol-1-yl,    3-(propan-2-yl)-5-(trifluoromethyl)-1H-pyrazol-1-yl,    3-tert-butyl-5-(pentafluoroethyl)-1H-pyrazol-1-yl,    3-tert-butyl-5-(trifluoromethyl)-1H-pyrazol-1-yl,    5-ethyl-3-(trifluoromethyl)-1H-pyrazol-1-yl,    5-tert-butyl-3-(pentafluoroethyl)-1H-pyrazol-1-yl,    5-tert-butyl-3-(trifluoromethyl)-1H-pyrazol-1-yl, 2H-indazol-2-yl,    1,3-benzodioxol-5-yl or 1H-benzimidazol-2-yl,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

Extraordinary preference is furthermore given to compounds of theformula (I) in which

-   R³ represents 2,4-dichlorophenyl, 2,4-dimethoxyphenyl,    2,5-dimethoxyphenyl, 2-methoxyphenyl, 2-methylphenyl,    3,5-dimethylisoxazol-4-yl, 3-methylpyridin-2-yl, quinolin-8-yl,    morpholin-4-yl, naphthalene, tert-butyl, trimethylsilyl,    1,2,3,4-tetrahydronaphthalen-1-yl, cyclohexyl, 2-bromophenyl,    2-chlorophenyl, 2-chloro-6-fluorophenyl, 2,6-difluorophenyl,    where the other substituents have one or more of the meanings    mentioned above,    and to the agrochemically active salts thereof.

The radical definitions given above can be combined with one another asdesired. Moreover, individual definitions may not apply.

Depending on the nature of the substituents defined above, the compoundsof the formula (I) have acidic or basic properties and can form salts,if appropriate also inner salts, or adducts with inorganic or organicacids or with bases or with metal ions. If the compounds of the formula(I) carry amino, alkylamino or other groups which induce basicproperties, these compounds can be reacted with acids to give salts, orthey are directly obtained as salts in the synthesis. If the compoundsof the formula (I) carry hydroxyl, carboxyl or other groups which induceacidic properties, these compounds can be reacted with bases to givesalts. Suitable bases are, for example, hydroxides, carbonates,bicarbonates of the alkali metals and alkaline earth metals, inparticular those of sodium, potassium, magnesium and calcium,furthermore ammonia, primary, secondary and tertiary amines having(C₁-C₄)-alkyl groups, mono-, di- and trialkanolamines of(C₁-C₄)-alkanols, choline and also chlorocholine.

The salts obtainable in this manner also have fungicidal, herbicidal andinsecticidal properties.

Examples of inorganic acids are hydrohalic acids, such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulphuric acid, phosphoric acid and nitric acid, and acidic salts, suchas NaHSO₄ and KHSO₄. Suitable organic acids are, for example, formicacid, carbonic acid and alkanoic acids, such as acetic acid,trifluoroacetic acid, trichloroacetic acid and propionic acid, and alsoglycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid,benzoic acid, cinnamic acid, oxalic acid, alkylsulphonic acids(sulphonic acids having straight-chain or branched alkyl radicals of 1to 20 carbon atoms), arylsulphonic acids or aryldisulphonic acids(aromatic radicals, such as phenyl and naphthyl, which carry one or twosulphonic acid groups), alkylphosphonic acids (phosphonic acids havingstraight-chain or branched alkyl radicals of 1 to 20 carbon atoms),arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, suchas phenyl and naphthyl, which carry one or two phosphonic acidradicals), where the alkyl and aryl radicals may carry furthersubstituents, for example p-toluenesulphonic acid, salicylic acid,p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid,etc.

Suitable metal ions are in particular the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminium, tin and lead, and also ofthe first to eighth transition group, in particular chromium, manganese,iron, cobalt, nickel, copper, zinc and others. Particular preference isgiven to the metal ions of the elements of the fourth period. Here, themetals can be present in various valencies that they can assume.

Optionally substituted groups may be mono- or polysubstituted, where inthe case of polysubstitution the substituents may be identical ordifferent.

In the definitions of the symbols given in the formulae above,collective terms were used which are generally representative for thefollowing substituents:

halogen: fluorine, chlorine, bromine and iodine;alkyl: saturated, straight-chain or branched hydrocarbon radicals having1 to 8 carbon atoms, for example (but not limited thereto) C₁-C₆-alkyl,such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and1-ethyl-2-methylpropyl;alkenyl: unsaturated, straight-chain or branched hydrocarbon radicalshaving 2 to 8 carbon atoms and a double bond in any position, forexample (but not limited thereto) C₂-C₆-alkenyl, such as ethenyl,1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;alkynyl: straight-chain or branched hydrocarbon groups having 2 to 8carbon atoms and a triple bond in any position, for example (but notlimited thereto) C₂-C₆-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl,1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl,1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;alkoxy: saturated, straight-chain or branched alkoxy radicals having 1to 8 carbon atoms, for example (but not limited thereto) C₁-C₆-alkoxy,such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy,1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy,1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy,1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy,1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy,2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy,1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy,1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and1-ethyl-2-methylpropoxy;alkylthio: saturated, straight-chain or branched alkylthio radicalshaving 1 to 8 carbon atoms, for example (but not limited thereto)C₁-C₆-alkylthio, such as methylthio, ethylthio, propylthio,1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio,1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio,3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio,1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio,2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio,1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio,2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio,1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio,1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and1-ethyl-2-methylpropylthio;alkoxycarbonyl: an alkoxy group having 1 to 6 carbon atoms (as mentionedabove) which is attached to the skeleton via a carbonyl group (—CO—);alkylsulphinyl: saturated, straight-chain or branched alkylsulphinylradicals having 1 to 8 carbon atoms, for example (but not limitedthereto) C₁-C₆-alkylsulphinyl, such as methylsulphinyl, ethylsulphinyl,propylsulphinyl, 1-methylethylsulphinyl, butylsulphinyl,1-methylpropylsulphinyl, 2-methylpropylsulphinyl,1,1-dimethylethylsulphinyl, pentylsulphinyl, 1-methylbutylsulphinyl,2-methylbutylsulphinyl, 3-methylbutylsulphinyl,2,2-dimethylpropylsulphinyl, 1-ethylpropylsulphinyl, hexylsulphinyl,1,1-dimethylpropylsulphinyl, 1,2-dimethylpropylsulphinyl,1-methylpentylsulphinyl, 2-methylpentyl sulphinyl,3-methylpentylsulphinyl, 4-methylpentylsulphinyl,1,1-dimethylbutylsulphinyl, 1,2-dimethylbutylsulphinyl,1,3-dimethylbutylsulphinyl, 2,2-dimethylbutylsulphinyl,2,3-dimethylbutylsulphinyl, 3,3-dimethylbutylsulphinyl,1-ethylbutylsulphinyl, 2-ethylbutylsulphinyl,1,1,2-trimethylpropylsulphinyl, 1,2,2-trimethylpropylsulphinyl,1-ethyl-1-methylpropylsulphinyl and 1-ethyl-2-methylpropylsulphinyl;alkylsulphonyl: saturated, straight-chain or branched alkylsulphonylradicals having 1 to 8 carbon atoms, for example (but not limitedthereto) C₁-C₆-alkylsulphonyl, such as methylsulphonyl, ethylsulphonyl,propylsulphonyl, 1-methylethylsulphonyl, butylsulphonyl,1-methylpropylsulphonyl, 2-methylpropylsulphonyl,1,1-dimethylethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl,2-methylbutylsulphonyl, 3-methylbutylsulphonyl,2,2-dimethylpropylsulphonyl, 1-ethylpropylsulphonyl, hexylsulphonyl,1,1-dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl,1-methylpentylsulphonyl, 2-methylpentylsulphonyl,3-methylpentylsulphonyl, 4-methylpentylsulphonyl,1,1-dimethylbutylsulphonyl, 1,2-dimethylbutylsulphonyl,1,3-dimethylbutylsulphonyl, 2,2-dimethylbutylsulphonyl,2,3-dimethylbutylsulphonyl, 3,3-dimethylbutylsulphonyl,1-ethylbutylsulphonyl, 2-ethylbutylsulphonyl,1,1,2-trimethylpropylsulphonyl, 1,2,2-trimethylpropylsulphonyl,1-ethyl-1-methylpropylsulphonyl and 1-ethyl-2-methylpropylsulphonyl;cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 10carbon ring members, for example (but not limited thereto) cyclopropyl,cyclopentyl and cyclohexyl;haloalkyl: straight-chain or branched alkyl groups having 1 to 8 carbonatoms (as mentioned above), where in these groups some or all of thehydrogen atoms may be replaced by halogen atoms as mentioned above, forexample (but not limited thereto) C₁-C₃-haloalkyl, such as chloromethyl,bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl,1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and1,1,1-trifluoroprop-2-yl;haloalkoxy: straight-chain or branched alkoxy groups having 1 to 8carbon atoms (as mentioned above), where in these groups some or all ofthe hydrogen atoms may be replaced by halogen atoms as mentioned above,for example (but not limited thereto) C₁-C₃-haloalkoxy, such aschloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy,fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy,dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy,1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy;haloalkylthio: straight-chain or branched alkylthio groups having 1 to 8carbon atoms (as mentioned above), where in these groups some or all ofthe hydrogen atoms may be replaced by halogen atoms as mentioned above,for example (but not limited thereto) C₁-C₃-haloalkylthio, such aschloromethylthio, bromomethylthio, dichloromethylthio,trichloromethylthio, fluoromethylthio, difluoromethylthio,trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio,chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio,1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio,2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio,2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio,2,2,2-trichloroethylthio, pentafluoroethylthio and1,1,1-trifluoroprop-2-ylthio;heteroaryl: a 5 or 6-membered completely unsaturated monocyclic ringsystem which contains one to four heteroatoms from the group consistingof oxygen, nitrogen and sulphur; if the ring contains a plurality ofoxygen atoms, these are not directly adjacent;5-membered heteroaryl which contains one to four nitrogen atoms or oneto three nitrogen atoms and one sulphur or oxygen atom: 5-memberedheteroaryl groups which, in addition to carbon atoms, may contain one tofour nitrogen atoms or one to three nitrogen atoms and one sulphur oroxygen atom as ring members, for example (but not limited thereto)2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl,3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl,5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl,1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and1,3,4-triazol-2-yl;5-membered heteroaryl which is attached via nitrogen and contains one tofour nitrogen atoms, or benzo-fused 5-membered heteroaryl which isattached via nitrogen and contains one to three nitrogen atoms:5-membered heteroaryl groups which, in addition to carbon atoms, maycontain one to four nitrogen atoms and one to three nitrogen atoms,respectively, as ring members and in which two adjacent carbon ringmembers or a nitrogen and an adjacent carbon ring member may be bridgedby a buta-1,3-dien-1,4-diyl group in which one or two carbon atoms maybe replaced by nitrogen atoms, where these rings are attached to theskeleton via one of the nitrogen ring members, for example (but notlimited thereto) 1-pyrrolyl, 1-pyrazolyl, 1,2,4-triazol-1-yl,1-imidazolyl, 1,2,3-triazol-1-yl, 1,3,4-triazol-1-yl;6-membered heteroaryl which contains one to four nitrogen atoms:6-membered heteroaryl groups which, in addition to carbon atoms, maycontain one to three or one to four nitrogen atoms as ring members, forexample (but not limited thereto) 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl,5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and1,2,4,5-tetrazin-3-yl;benzo-fused 5-membered heteroaryl which contains one to three nitrogenatoms or one nitrogen atom and one oxygen or sulphur atom: for example(but not limited thereto) 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl,1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl,1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl,benzimidazol-5-yl, 1H-indazol-1-yl, 1H-indazol-3-yl, 1H-indazol-4-yl,1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl, 2H-indazol-2-yl,1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl,1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl,1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl,1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl,1,3-benzothiazol-2-yl and 1,3-benzoxazol-2-yl,benzo-fused 6-membered heteroaryl which contains one to three nitrogenatoms: for example (but not limited thereto) quinolin-2-yl,quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl,quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl,isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl,and isoquinolin-8-yl;heterocyclyl: a three- to fifteen-membered saturated or partiallyunsaturated heterocycle which contains one to four heteroatoms from thegroup consisting of oxygen, nitrogen and sulphur: mono-, bi- ortricyclic heterocycles which contain, in addition to carbon ringmembers, one to three nitrogen atoms and/or one oxygen or sulphur atomor one or two oxygen and/or sulphur atoms; if the ring contains aplurality of oxygen atoms, these are not directly adjacent; such as, forexample (but not limited thereto), oxiranyl, aziridinyl,2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl,4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl,4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl,4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl,5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl,2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl,2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl,2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl,2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl,2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl,2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl,2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl,2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl,2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl,2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl,3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl,3,4-dihydropyrazol-5-yl, 4,5-dihydroopyrazol-1-yl,4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl,4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl,2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl,3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl,2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl,2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl,3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl,4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl,1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl;leaving group: S_(N)1 or S_(N)2 leaving group, for example halogen(chlorine, bromine, iodine), alkylsulphonates (—OSO₂-alkyl, for example—OSO₂CH₃, —OSO₂CF₃) or arylsulphonates (—OSO₂-aryl, for example —OSO₂Ph,—OSO₂PhMe).

Not included are combinations which contradict natural laws and whichthe person skilled in the art would therefore have excluded based on hisexpert knowledge. Excluded are, for example, ring structures havingthree or more adjacent oxygen atoms.

The present invention furthermore relates to a process for preparing theheterocyclyl-substituted thiazoles of the formula (I) according to theinvention, comprising at least one of steps (a) to (u) below:

-   (a) the conversion of compounds of the formula (VII) in the presence    of an organometallic compound R⁹-M and, if appropriate, in the    presence of a solvent, into compounds of the formula (VIII),    according to the reaction scheme below (Scheme 1):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl,        C₁-C₄-alkoxycarbonyl and benzyloxycarbonyl,    -   M= for example MgCl, MgBr, MgI, L¹,    -   R⁹═C₁-C₄-alkyl or C₃-C₆-cycloalkyl,    -   W, X, and R² are as defined for formula (I) above.

-   (b) the reaction of alcohols of the formula (VIII) with an oxidizing    agent in the presence of a solvent, to give ketones of the formula    (IX), according to the reaction scheme below (Scheme 2):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl        and C₁-C₄-alkoxycarbonyl,    -   R⁹═C₁-C₄-alkyl or C₃-C₆-cycloalkyl,    -   W, X, and R² are as defined for formula (I) above.

-   (c) the conversion of ketones of the formula (IX) in the presence of    a base or an acid and, if appropriate, a solvent, into compounds of    the formula (IVb), according to the reaction scheme below (Scheme    3):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl        and C₁-C₄-alkoxycarbonyl,    -   L²=—CR⁹═CR⁹—,    -   W, X, L³, R², R³ and R⁹ are as defined for formula (I) above.

-   (d) the conversion of aldehydes of the formula (VII) in the presence    of a base or an acid and, if appropriate, a solvent, into compounds    of the formula (IVb), according to the reaction scheme below (Scheme    4):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl        and C₁-C₄-alkoxycarbonyl,    -   L²=—CR⁹═CR⁹—,    -   W, X, L³, R², R³ and R⁹ are as defined for formula (I) above.

-   (e) the conversion of aldehydes of the formula (VII) in the presence    of a base and, if appropriate, a solvent, into alkynes of the    formula (X) according to the reaction scheme below (Scheme 5):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl        and C₁-C₄-alkoxycarbonyl,    -   W, X and R² are as defined for formula (I) above.

-   (f) the reaction of alkynes of the formula (X) with an R³-L³-halide    in an optionally catalyzed C—C coupling reaction in the presence of    a base and, if appropriate, a solvent, to give compounds of the    formula (IVc), according to the reaction scheme below (Scheme 6):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl        and C₁-C₄-alkoxycarbonyl,    -   Hal=Cl, Br or I,    -   L²=—C≡C—,    -   W, X, L³, R² and R³ are as defined for formula (I) above.

-   (g) the reaction of alkynes of the formula (X) with a trialkylsilyl    chloride (R¹⁰R¹¹R¹²)SiCl or trialkylsilyl triflate    (R¹⁰R¹¹R¹²)SiOSO₂CF₃ or other known silylating agents in the    presence of a base and, if appropriate, a solvent, to give compounds    of the formula (XI), according to the reaction scheme below (Scheme    7):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl        and C₁-C₄-alkoxycarbonyl,    -   R¹⁰, R¹¹ and R¹²═C₁-C₄ alkyl or phenyl,    -   W, X and R² are as defined for formula (I) above.

-   (h) the reaction of alkynes of the formula (XI) with a compound    R³-L³-Hal, if appropriate in the presence of a catalyst, in the    presence of a base and, if appropriate, a solvent, to give compounds    of the formula (IVc), according to the reaction scheme below (Scheme    8):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl        and C₁-C₄-alkoxycarbonyl,    -   Hal=Cl, Br or I,    -   R²=hydrogen, C₁-C₂-alkyl or C₁-C₂-haloalkyl,    -   L²=—C≡C—,    -   R¹⁰, R¹¹ and R¹²═C₁-C₄-alkyl or phenyl,    -   W, X, L³ and R³ are as defined for formula (I) above.

-   (i) the reaction of thioamides of the formula (V) with compounds of    the formula (VIa) or (VIb) in the presence of a base and, if    appropriate, in the presence of a solvent, to give compounds of the    formula (IVa) or (IVb), according to the reaction scheme below    (Scheme 9):

where

-   -   PG=unsubstituted or substituted phenylmethyl (where the        substituents independently of one another are selected from the        group consisting of methyl, methoxy, nitro, dioxolano), acetyl,        C₁-C₄-alkoxycarbonyl and benzyloxycarbonyl,    -   Hal=Cl, Br or I,    -   L²=—C(R⁸)₂—C(R⁸)₂— for compounds of the formula (IVa) and (VIa),    -   L²=—CR⁹═CR⁹— for compounds of the formula (IVb) and (VIb),    -   W, X, L³, R², R³, R⁸ and R⁹ are as defined for formula (I)        above.

-   (j) the conversion of compounds of the formula (IVb) or (IVc) in the    presence of hydrogen, a catalyst and, if appropriate, a solvent,    into compounds of the formula (IVa), according to the reaction    scheme below, (Scheme 10):

where

-   -   PG=acetyl or C₁-C₄-alkoxycarbonyl,    -   L²=—C(R⁸)₂—C(R⁸)₂— for compounds of the formula (IVa),    -   L²=—CR⁹═CR⁹— for compounds of the formula (IVb),    -   L²=—C≡C— for compounds of the formula (IVc),    -   W, X, L³, R², R³, R⁸ and R⁹ are as defined for formula (I)        above.

-   (k) the conversion of compounds of the formula (IV), if appropriate    in the presence of a solvent and, if appropriate, in the presence of    an acid or, if appropriate, in the presence of a base or, if    appropriate, in the presence of a source of hydrogen, into compounds    of the formula (II), according to the reaction scheme below (Scheme    11):

where

-   -   PG=acetyl, C₁-C₄-alkoxycarbonyl or benzyloxycarbonyl,    -   W, X, L², L³, R², and R³ are as defined for formula (I) above.

-   (l) the conversion of compounds of the formula (IIa′) in the    presence of a halogenating agent, if appropriate in the presence of    an acid and a solvent, into compounds of the formula (IIa),    according to the reaction scheme below (Scheme 12):

where

-   -   L²=—C(R⁸)₂—C(R⁸)₂—,    -   R²═I, Br or Cl for compounds of the formula (IIa),    -   R²=hydrogen for compounds of the formula (IIa′),    -   W, X, L³, R³ and R⁸ are as defined for formula (I) above.

-   (m) the reaction of compounds of the formula (III) with compounds of    the formula (II), if appropriate in the presence of a coupling    agent, a base and a solvent, to give compounds of the formula (I),    according to the reaction scheme below (Scheme 13):

where

-   -   B═OH, chlorine, bromine or iodine,    -   Y=oxygen,    -   A, W, X, L¹, L², L³, R², and R³ are as defined for formula (I)        above.

-   (n) the conversion of compounds of the formula (I) in the presence    of a sulphurizing agent and, if appropriate, in the presence of a    solvent, into compounds of the formula (I), according to the    reaction scheme below (Scheme 14):

where

-   -   A, W, X, L¹, L², L³, R², and R³ are as defined for formula (I)        above.

-   (o) the conversion of aldehydes of the formula (XII) in the presence    of a base and, if appropriate, a solvent, into alkynes of the    formula (XIII), according to the reaction scheme below (Scheme 17):

where

-   -   A, W, X, Y, L¹ and R² are as defined for formula (I) above.

-   (p) the reaction of alkynes of the formula (XIII) with a    trialkylsilyl chloride (R¹⁰R¹¹R¹²)SiCl or trialkylsilyl triflate    (R¹⁰R¹¹R¹²)SiOSO₂CF₃ or other known silylating agents in the    presence of a base and, if appropriate, a solvent, to give compounds    of the formula (XIV), according to the reaction scheme below (Scheme    18):

where

-   -   R¹⁰, R¹¹ and R¹²═C₁-C₄ alkyl or phenyl,    -   A, W, X, Y, L¹ and R² are as defined for formula (I) above.

-   (q) the reaction of alkynes of the formula (XIII) with an    R³-L³-halide in an optionally catalyzed C—C coupling reaction in the    presence of a base and, if appropriate, a solvent, to give compounds    of the formula (Ic), according to the reaction scheme below (Scheme    19):

where

-   -   Hal=Cl, Br or I,    -   L²=—C≡C—,    -   A, W, X, Y, L¹ L³, R² and R³ are as defined for formula (I)        above.

-   (r) the reaction of alkynes of the formula (XIV) with a compound    R³-L³-Hal, if appropriate in the presence of a catalyst, in the    presence of a base and, if appropriate, a solvent, to give compounds    of the formula (Ic), according to the reaction scheme below (Scheme    20):

where

-   -   Hal=Cl, Br or I,    -   L²=—C≡C—,    -   R¹⁰, R¹¹ and R¹²═C₁-C₄ alkyl or phenyl,    -   A, W, X, Y, L¹ L³, R² and R³ are as defined for formula (I)        above.

-   (s) the conversion of aldehydes of the formula (XII) in the presence    of a base or an acid and, if appropriate, a solvent, into compounds    of the formula (Ib), according to the reaction scheme below (Scheme    21):

where

-   -   L²=—CR⁹═CR⁹—,    -   A, W, X, Y, L¹ L³, R², R³ and R⁹ are as defined for formula (I)        above.

-   (t) the conversion of compounds of the formula (Ic) in the presence    of hydrogen, a catalyst and, if appropriate, a solvent, into    compounds of the formula (Ib), according to the reaction scheme    below (Scheme 22):

where

-   -   L²=—CR⁹═CR⁹— for compounds of the formula (Ib),    -   L²=—C≡C— for compounds of the formula (Ic),    -   A, W, X, Y, L¹ L³, R², R³ and R⁹ are as defined for formula (I)        above.

-   (u) the conversion of compounds of the formula (Ib) or (Ic) in the    presence of hydrogen, a catalyst and, if appropriate, a solvent,    into compounds of the formula (Ia), according to the reaction scheme    below (Scheme 23):

where

-   -   L²=—C(R⁸)₂—C(R⁸)₂— for compounds of the formula (Ia),    -   L²=—CR⁹═CR⁹— for compounds of the formula (Ib),    -   L²=—C≡C— for compounds of the formula (Ic),    -   A, W, X, Y, L¹ L³, R², R³, R⁸ and R⁹ are as defined for        formula (I) above.

A general summary of the synthesis paths is shown in Schemes 15 and 24.

A compound of the general formula (V) is reacted with a compound of theformula (VIa) or (VIb) to give a cyclic compound of the formula (IVa) or(IVb) (Scheme 9). Another option of preparing compounds of the formula(IV) is to start with compounds of the formula (VII). These can besubjected to a reaction with a substrate of the general formula R⁹-M(Scheme 1). A secondary alcohol of the formula (VIII) is formed, whichis then oxidized, giving a compound of the formula (IX) (Scheme 2). Acompound of the formula (VII) or (IX) is subjected to an olefination toprepare a compound of the formula (IVb) (Scheme 3 and Scheme 4). Anotherpossible route of preparing compounds of the formula (IV) also startswith a compound of the formula (VII). A compound of the formula (VII) isalkynylated to prepare a terminal alkyne of the general formula (X)(Scheme 5). A transition metal-catalyzed C—C coupling reaction of acompound of the formula (X) with a halide of the formula R³-L³-Hal givesa compound of the formula (IVc) (Scheme 6). A compound of the formula(X) can also be provided with a silyl group, which leads to a compoundof the formula (XI) (Scheme 7). This is then subjected to a transitionmetal-catalyzed coupling reaction, namely with a substrate of thegeneral formula R³-L³-Hal, to prepare a compound of the formula (IVc)(Scheme 8). Using hydrogen, the double and triple bonds of a compound ofthe formula (IVb) and (IVc) can be hydrogenated, to give a compound ofthe formula (IVa) (Scheme 10). The protective group of a compound of theformula (IV), which is labelled PG, is then removed, forming a compoundof the formula (II) or the corresponding salt (Scheme 11). A compound ofthe formula (IIa′) can be halogenated to form a compound of the formula(IIa) (Scheme 12). A compound of the formula (II) or a correspondingsalt is coupled with a substrate of the formula (III), which allows thepreparation of a compound of the formula (I) (Scheme 13). A compound ofthe formula (I) is treated with a sulphurizing agent to generate acompound of the formula (I) (Scheme 14).

Another possible route of preparing compounds of the formula (I) startswith a compound of the formula (XII) (Scheme 24). A compound of theformula (XII) is alkynylated to prepare a terminal alkyne of the generalformula (XIII) (Scheme 17). A transition metal-catalyzed C—C couplingreaction of a compound of the formula (XIII) with a halide of theformula R³-L³-Hal gives a compound of the formula (Ic) (Scheme 19). Acompound of the formula (XIII) can also be provided with a silyl group,which leads to a compound of the formula (XIV) (Scheme 18). This is thensubjected to a transition metal-catalyzed coupling reaction, namely witha substrate of the general formula R³-L³-Hal, to prepare a compound ofthe formula (Ic) (Scheme 20). A compound of the formula (XII) issubjected to an olefination to prepare a compound of the formula (Ib)(Scheme 21). Using hydrogen, the triple bond of a compound of theformula (Ic) can be hydrogenated, to give a compound of the formula (Ib)(Scheme 22). Using hydrogen, the double and triple bonds of a compoundof the formula (Ib) and (Ic) can be hydrogenated, to give a compound ofthe formula (Ia) (Scheme 23).

One way of preparing the intermediate (VIII) from compound (VII) isshown in Scheme 1.

Starting materials of the formula (VIII) are prepared from the aldehyde(VII) by addition of an organometallic reagent R⁹-M (for example M=Mg,Li). The alcohols (VIII) are preferably prepared by addition of aGrignard reagent R⁹—MgX (X═Cl, Br, or I) to compounds (VII) intetrahydrofuran at −78° C., under an inert atmosphere (see, for example,WO 07/039,177).

The aldehyde (VII) is commercially available (for example Maybridge) orcan be prepared from commercially available precursors according toprocedures described in the literature. The aldehyde (VII) is prepared,for example, from the corresponding methyl or ethyl ester (XV) byreduction with lithium aluminium hydride in tetrahydrofuran at 0° C.,followed by an oxidation of the corresponding alcohol with Dess-Martinreagent at room temperature in dichloromethane (see, for example, WO07/147,336 and WO 07/039,177 for the reduction with lithium aluminiumhydride and J. Am. Chem. Soc. 1978, 100, 300-301; 1979, 101, 5294-5299;1991, 113, 7277-7287 for the oxidation using Dess-Martin reagent).

where

-   -   R═H or acid-labile amine protective groups, such as, for        example, t-butoxycarbonyl (tBoc) or benzyloxycarbonyl (Cbz) or a        benzyl protective group, such as, for example, benzyl (Bn).    -   W and X are as defined for formula (I) above.

Methyl or ethyl esters (XV) are known and can be prepared fromcommercially available precursors according to methods described in theliterature, for example from nitriles of the formula (XVI), carboxylicacids of the formula (XVII), carbonyl chlorides of the formula (XVIII),amides of the formula (XIX) or thioamides of the formula (V) (FIG. 2). Apreferred method is the Hantzsch thiazole synthesis. Starting from (V)and commercially available ethyl or methyl halpyruvate in ethanol or inN,N-dimethylformamide in the presence of, for example, triethylamine atroom temperature (for examples see WO 07/014290 and the references citedtherein).

where

-   -   R═H or acid-labile amine protective groups, such as, for        example, t-butoxycarbonyl (tBoc) or benzyloxycarbonyl (Cbz) or a        benzyl protective group, such as, for example, benzyl (Bn).    -   W and X are as defined for formula (I) above.

One way of preparing intermediate (IX) from compound (VIII) is shown inScheme 2.

Compounds of the formula (IX) are prepared by oxidation of the alcohol(VIII). There are numerous methods for preparing ketones from secondaryalcohols in the literature (see, “Oxidation of Alcohols to Aldehydes andKetones”, Gabriel Tojo, Marcos Fernández, Springer Berlin, 2006, 1-97,and the literature cited therein). The oxidation is preferably carriedout under Swern conditions or using Dess-Martin periodinane (see, forexample, J. Am. Chem. Soc. 1978, 100, 300-301). Suitable solvents areall solvents which for their part are not oxidized by the oxidizingagent, such as, for example, dichloromethane, chloroform oracetonitrile, if appropriate in the presence of a reaction auxiliary,for example an acid (for example sulphuric acid or hydrochloric acid) orelse a base (for example triethylamine or pyridine).

One way of obtaining intermediate (IX) from compound (VIII) is, forexample, using Dess-Martin periodinane (15% in dichloromethane,commercially available, for example, from Acros).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, cyclic and acyclicethers (for example diethyl ether, tetrahydrofuran, dioxane), aromatichydrocarbons (for example benzene, toluene, xylene), halogenatedhydrocarbons (for example dichloromethane, chloroform, carbontetrachloride), halogenated aromatic hydrocarbons (for examplechlorobenzene, dichlorobenzene), nitriles (for example acetonitrile),carboxylic esters (for example ethyl acetate), amides (for exampleN,N-dimethylformamide, N,N-dimethylacetamide), dimethyl sulphoxide,1,3-dimethyl-2-imidazolinone and water, and the reaction can be carriedout in mixtures of two or more of these solvents.

The starting materials are employed in equimolar amounts; however, theoxidizing agent can, if required, also be used in excess. The reactionis usually carried out at temperatures of 0° C.-100° C. and preferablyat room temperature, but it can also be carried out at the refluxtemperature of the reaction mixture. The reaction time varies dependingon the scale of the reaction and the reaction temperature, but isgenerally between a couple of minutes and 48 hours.

After the reaction has ended, compound (IX) is removed from the reactionmixture using one of the customary separation techniques. If required,the compounds are purified by recrystallisation, distillation orchromatography, or they can, if appropriate, also be used for the nextstep without prior purification.

One way of preparing the intermediate (IVb) from compound (IX) or (VII)is shown in Schemes 3 and 4.

Ketones of the formula (IX) or aldehydes of the formula (VII) areconverted into (Z)- or (E)-(IVb), for example by a Wittig orHorner-Wadsworth-Emmons olefination (see, for example, Chem. Rev. 1989,89, 863-927 and the references cited therein) or, for example, by aJulia olefination (see, for example, Tetrahedron Lett., 1973, 14,4833-4836) or, for example, by a Peterson olefination (see, for example,J. Org. Chem. 1968, 33, 780). Preferably, the olefination is carried outunder Wittig or Horner-Wadsworth-Emmons conditions.

The reagents, such as phosphonium salts and phosphonate reagents, areeither commercially available or can be obtained in the manner describedin the literature (see, for example, “The Chemistry of OrganophosphorusCompounds”; John Wiley & Sons, 1994, Vol 3, 45-184, and the literaturecited therein).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, cyclic and acyclicethers (for example diethyl ether, tetrahydrofuran, dioxane), aromatichydrocarbons (for example benzene, toluene, xylene), halogenatedhydrocarbons (for example dichloromethane, chloroform, carbontetrachloride), halogenated aromatic hydrocarbons (for examplechlorobenzene, dichlorobenzene), and the reaction can be carried out inmixtures of two or more of these solvents. The preferred solvents aretetrahydrofuran and toluene.

Suitable for use as bases are the bases usually employed in theolefination reactions mentioned above, for example NaH, tBuOK, nBuLi,(see, for example, Rev. 1989, 89, 863-927 and the references citedtherein). Suitable acids are those which are usually employed inolefination reactions, such as for example, sulphonic acids or sulphuricacid.

The starting materials are employed in equimolar amounts; however, thephosphonium salts or phosphonates can, if required, also be used inexcess. The reaction is usually carried out at temperatures of 0°C.-100° C. and preferably at 0° C.-25° C., but it can also be carriedout at the reflux temperature of the reaction mixture. The reaction timevaries depending on the scale of the reaction and the reactiontemperature, but is generally between a couple of minutes and 48 hours.

After the reaction has ended, compounds (IVb) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

One way of preparing the intermediate (X) from compound (VII) is shownin Scheme 5.

It is known from the literature that alkynylations of aldehydes can becarried out by a Corey-Fuchs reaction (Tetrahedron Lett. 1972, 36,3769-3772) or a Seyferth-Gilbert homologation (see, for example, J. Org.Chem., 1996, 61, 2540-2541). Alternatively, the alkyne (X) can also beprepared from the aldehyde (VII) using Bestmann-Ohira's reagentanalogously to the literature procedures (see, for example, Synthesis2004, 1, 59-62).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, cyclic and acyclicethers (for example diethyl ether, tetrahydrofuran, dioxane), aromatichydrocarbons (for example benzene, toluene, xylene), halogenatedhydrocarbons (for example dichloromethane, chloroform, carbontetrachloride) and halogenated aromatic hydrocarbons (for examplechlorobenzene, dichlorobenzene), and the reaction can be carried out inmixtures of two or more of these solvents. The preferred solvents aretetrahydrofuran and toluene.

All known bases can be used in the reaction; however, preference isgiven to using alkali metal and alkaline earth metal oxides, hydroxidesand carbonates. At least one equivalent of the base has to be added tothe Bestmann-Ohira's reagent and, if required, the base may be used inexcess.

The starting materials are employed in equimolar amounts; however, theBestmann-Ohira's reagent can, if required, also be used in excess. Thereaction is usually carried out at temperatures of 0° C.-60° C. andpreferably at 0° C.-40° C., but it can also be carried out at the refluxtemperature of the reaction mixture. The reaction time varies dependingon the scale of the reaction and the reaction temperature, but isgenerally between a couple of minutes and 48 hours.

After the reaction has ended, the compounds (VIc) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

Analogously to the method described above, the compounds (XIII) can besynthesized from the corresponding compounds (XII) as shown in Scheme17. The aldehyde (XII) can be prepared according to procedures knownfrom the literature (for examples, see WO 08/013,925, WO 08/013,622 andthe references cited therein).

One way of preparing the intermediate (IVc) from compound (X) is shownin Scheme 6.

A compound of the general formula (IVc) can be obtained from an alkyneof the general formula (X) by palladium-catalyzed cross-couplinganalogously to procedures described in the literature (see, for example,J. Am. Chem. Soc. 2003, 125, 13642-13643, Synlett. 2006, 18, 2941-2946),namely using a halide of the formula R³-L³-Hal, where the primary halideis reacted in the presence of a catalyst such as, for example,[(π-allyl)PdCl]₂, Pd(OAc)₂, PdCl₂(CH₃CN)₂, Pd(PPh₃)₄ or PdCl₂(PPh₃)₂and, if appropriate, in the presence of other cocatalysts, such as, forexample, CuI, Cs₂CO₃ and 1,3-bis(1-adamantyl)imidazolium chloride, forexample in a solvent mixture of DMF and diethyl ether at 0-80° C.

Halides of the formula R³-L³-Hal are either commercially available orcan be obtained by methods known from the literature.

Alternatively, the terminal alkyne can also be provided with aprotective group, such as for example, by reaction with benzyl chloridein the presence of a palladium(II) catalyst, such as, for example,Pd(OAc)₂ or PdCl₂(CH₃CN)₂, and caesium carbonate and also2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, intetrahydrofuran or acetonitrile at 0-80° C.

After the reaction has ended, the compounds (IVc) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

Analogously to the method described above, the compounds (Ic) can besynthesized from corresponding compounds (XIII) as shown in Scheme 19.

One way of preparing the intermediate (XI) from compound (X) is shown inScheme 7.

To form a direct bond between the triple bond (L² is —C≡C—) and R³, ismay be necessary to silylate the terminal alkyne prior to thepalladium-catalyzed coupling reaction. Silylations of terminal alkynesare carried out using one of the known methods for silylating terminalalkynes, such as, for example, by adding a base (such as, for example,lithium hexamethyldisilazide) at −78° C. in a polar aprotic solvent tothe terminal alkyne and capturing the resulting intermediate using, forexample, a silyl halide (CHEMBIOCHEM, 2001, 1, 69-75) or silyl triflate.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, cyclic and acyclicethers (for example diethyl ether, tetrahydrofuran, dioxane), aromatichydrocarbons (for example benzene, toluene, xylene), halogenatedhydrocarbons (for example dichloromethane, chloroform, carbontetrachloride) and halogenated aromatic hydrocarbons (for examplechlorobenzene, dichlorobenzene). The reaction can also be carried out inmixtures of two or more of these solvents. The preferred solvents aretetrahydrofuran and toluene.

All known bases may be employed; however, preference is given to usinglithium hexamethyldisilazide, sodium hexamethyldisilazide, potassiumhexamethyldisilazide and lithium diisopropylamide for the reaction. Atleast one equivalent of the base has to be added to the alkyne of thegeneral formula (X), and if required it may be used in excess.

At least one equivalent of silyl chloride or silyl triflate can be usedas source of the silyl group in the reaction.

The reaction is usually carried out at temperatures of −78° C.-100° C.and preferably at −20° C.-40° C., but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a couple of minutes and 48 hours.

After the reaction has ended, the compounds (XI) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

Analogously to the method described above, the compounds (XIV) can besynthesized from corresponding compounds (XIII) as shown in Scheme 18.

One way of preparing the intermediate (IVc) from compound (IX) is shownin Scheme 8.

A compound of the general formula (IVc) can be prepared from an alkyneof the general formula (XI) by palladium-catalyzed coupling reactions,such as, for example, the Sonogashira reaction (J. Med. Chem. 2006, 49,1080-1110), where the halide has the general formula R³-L³-halide inwhich L³ is a direct bond.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, cyclic and acyclicethers (for example diethyl ether, tetrahydrofuran, dioxane), aromatichydrocarbons (for example benzene, toluene, xylene), halogenatedhydrocarbons (for example dichloromethane, chloroform, carbontetrachloride), carboxylic esters (for example ethyl acetate), amides(for example N,N-dimethylformamide, N,N-dimethylacetamide), dimethylsulphoxide and 1,3-dimethyl-2-imidazolinone, and the reaction can becarried out in mixtures of two or more of these solvents. The preferredsolvent is N,N-dimethylformamide.

The reaction should be carried out in the presence of the followingadditives: triethylamine (at least one equivalent based on the compound(XI)), copper(I) iodide (at least 0.1 equivalent based on the compound(XI)) and a source of fluoride such as, for example,tetra-n-butylammonium fluoride (at least 1 equivalent based on thecompound (XI) or a slight excess).

A large number of the commercially available palladium(0) catalysts aresuitable for use in the reaction; however, preference is given to usingtetrakistriphenylphosphinepalladium (Aldrich) in the reaction. Theamount of catalyst used is at least 1% to an excess based on thestarting material (XI).

The reaction is usually carried out at temperatures of 25° C.-120° C.and preferably at 70° C.-90° C., but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a couple of minutes and 48 hours.

After the reaction has ended, the compounds (IVc) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

Analogously to the method described above, the compounds (Ic) can besynthesized from corresponding compounds (XIV) as shown in Scheme 20.

One way of synthesizing compounds of the formula (IVa) or (IVb) is shownin Scheme 9.

Thiocarboxamides (V) are either commercially available or can beobtained by methods known from the literature, for example bysulphurization of the corresponding commercially available carboxamideusing, for example, Lawesson's reagent (Org. Synth. Vol. 7, 1990, 372)at room temperature in a mixture of chloroform/dimethoxyethane (1/2.5).Here, PG represents a protective group as defined in Scheme 2.

α-Haloketones (VIa) and (VIb) are either commercially available or canbe obtained by methods known from the literature (for examples seeMolecules, 2003, 8, 793-865). Alternatively, enolates or silylenolethers prepared from (XIIa) or (XIIb) can be reacted with a halogensource to give α-haloketones (VIa) or (VIb), (J. Med. Chem. 2006, 49,7877-7886; J. Med. Chem. 2006, 49, 1080-1110; Org. Synth. Vol. 6, 1988,175; Org. Synth. Vol. 53, 1973, 111). (Scheme 16)

In Scheme 16,

Hal=Cl, Br or I,

L²=—C(R⁸)₂—C(R⁸)₂— for compounds of the formula (VIa) and (XIIa),L²=—CR⁹═CR⁹— for compounds of the formula (VIb) and (XIIb), L³, R², R³,R⁸ and R⁹ are as defined for formula (I) above.

The thiazoles (IVa) or (IVb) are obtained by a Hantzsch thiazolesynthesis from thiocarboxamides (V) and α-haloketones (VIa) or (VIb)(see, for example, “Comprehensive Heterocyclic Chemistry”, PergamonPress, 1984; Vol 6, pages 235-363, “Comprehensive Heterocyclic ChemistryII”, Pergamon Press, 1996; Vol 3, pages 373-474 and the references citedtherein, and WO 07/014,290).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),nitriles (for example acetonitrile), carboxylic esters (for exampleethyl acetate), amides (for example N,N-dimethylformamide,N,N-dimethylacetamide), dimethyl sulphoxide,1,3-dimethyl-2-imidazolinone, water and acetic acid, or the reaction canbe carried out in mixtures of two or more of these solvents. Thepreferred solvents are N,N-dimethylformamide and ethanol.

If appropriate, an auxiliary base such as, for example, triethylamine isused.

The starting materials are employed in equimolar amounts. However, (V)or (VI) can each also be used in excess. The reaction is usually carriedout at temperatures of 0° C.-100° C. and preferably at room temperature,but it can also be carried out at the reflux temperature of the reactionmixture. The reaction time varies depending on the scale of the reactionand the reaction temperature, but is generally between a couple ofminutes and 48 hours.

If required, the compounds are purified by recrystallization orchromatography, or they can, if appropriate, also be used in the nextstep without prior purification.

One way of preparing the intermediate (IVa) from compound (IVb) or (IVc)is shown in Scheme 10.

A triple bond or a double bond is converted by hydrogenation using asuitable catalyst into a single bond. A catalyst for the reaction inScheme 10 is selected from the hydrogenation catalysts known from theliterature (“Reductions in Organic Chemistry”, Milo{hacek over (s)}Hudlick{grave over (y)}, John Wiley & Sons, 1984), such as for example,palladium on activated carbon or Pearlmans catalyst (Pd(OH)₂ onactivated carbon). Using such a catalyst, it is possible to prepare acompound of the formula (IVa) from a compound of the formula (IVb) or(IVc).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane),aromatic hydrocarbons (for example benzene, toluene, xylene),halogenated hydrocarbons (for example dichloromethane, chloroform,carbon tetrachloride), halogenated aromatic hydrocarbons (for examplechlorobenzene, dichlorobenzene), nitriles (for example acetonitrile),carboxylic esters (for example ethyl acetate), amides (for exampleN,N-dimethylformamide, N,N-dimethylacetamide), dimethyl sulphoxide,1,3-dimethyl-2-imidazolinone, water and acetic acid, or the reaction canbe carried out in mixtures of two or more of these solvents. Thepreferred solvents are N,N-dimethylformamide and ethanol.

The amount of catalyst used is 0.1-90 mol % based on the startingmaterial; preference is given to using 1-30 mol % of the catalyst basedon the starting material. The reaction can be carried out atsuperatmospheric pressure (1-1000 bar) or, preferably, at atmosphericpressure. The reaction is usually carried out at temperatures of 0°C.-150° C. and preferably at room temperature, but it can also becarried out at the reflux temperature of the reaction mixture. Thereaction time varies depending on the scale of the reaction and thereaction temperature, but is generally between half an hour and 48hours.

After the reaction has ended, the compounds (IVa) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

One way of preparing the intermediate (II) from corresponding compounds(IV) is shown in Scheme 11.

A compound of the general formula (IV) is converted into a correspondingcompound of the general formula (II) by suitable methods, described inthe literature, for removing protective groups (“Protective Groups inOrganic Synthesis”; Third Edition; Theodora W. Greene, Peter G. M. Wuts;494-653, and the literature cited therein).

t-Butoxycarbonyl and benzyloxycarbonyl protective groups can be removedin an acidic medium (for example using hydrochloric acid ortrifluoroacetic acid). Acetyl protective groups can be removed underbasic conditions (using, for example, potassium carbonate or caesiumcarbonate). Benzylic protective groups can be removed hydrogenolyticallyusing hydrogen in the presence of a catalyst (for example palladium onactivated carbon).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),nitriles (for example acetonitrile), carboxylic esters (for exampleethyl acetate), amides (for example N,N-dimethylformamide,N,N-dimethylacetamide), dimethyl sulphoxide,1,3-dimethyl-2-imidazolinone, water and acetic acid, or the reaction canbe carried out in mixtures of two or more of these solvents.

Acids which can be used for this reaction of deprotectingt-butoxycarbonyl and benzyloxycarbonyl groups are, for example,trifluoroacetic acid, hydrochloric acid or other acids, as described inthe literature (for example “Protective Groups in Organic Synthesis”;Third Edition; Theodora W. Greene, Peter G. M. Wuts; pp. 494-653).

The reaction is usually carried out at temperatures of 0° C.-150° C. andpreferably at room temperature, but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between half an hour and 72 hours.

After the reaction has ended, the compounds (II) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification. Moreover, it is possible toisolate the compound of the general formula (II) as a salt, for exampleas a salt of hydrochloric acid or trifluoroacetic acid.

One way of preparing the intermediate (IIa) from compound (IIa′) isshown in Scheme 12.

A compound of the general formula (IIa) in which R²═Cl, Br and I isobtained by halogenation from a compound of the general formula (IIa′)where R²═H, see, for example, Org. Lett., 2005, 7(2), 299-301; Angew.Chem., Int. Ed., 2004, 43(34), 4471-4475; Eur. J. Org. Chem., 2002,(13), 2126-2135.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),carboxylic esters (for example ethyl acetate), amides (for exampleN,N-dimethylformamide, N,N-dimethylacetamide), dimethyl sulphoxide,1,3-dimethyl-2-imidazolinone, water and acetic acid, or the reaction canbe carried out in mixtures of two or more of these solvents.

Suitable for use as halogen source are, for example, N-bromosuccinimide,N-chlorosuccinimide, N-iodosuccinimide, pyridinium tribromide, bromine,iodine or chlorine.

If appropriate, a base, such as for example, lithium diisopropylamide orbutyllithium, may be used to lithiate the 5-position of the thiazoleprior to the addition of the electrophilic halogen source.

The reaction can, if appropriate, be carried out using an acid, such asfor example acetic acid, sulphuric acid, hydrobromic acid orhydrochloric acid.

The starting materials and the halogenating agent are employed inequimolar amounts. The halogenating agent can also be used in excess.The reaction is usually carried out at temperatures of 0° C.-60° C. andpreferably at 0° C.-30° C., but it can also be carried out at the refluxtemperature of the reaction mixture. The reaction time varies dependingon the scale of the reaction and the reaction temperature, but isgenerally between a couple of minutes and 48 hours.

After the reaction has ended, the compounds (II) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

One way of preparing compounds of the formula (I) in which Y=oxygen fromcorresponding compounds (II) is shown in Scheme 13.

Acid halides (III) (B=halogen) or the corresponding carboxylic acids(III) (B═OH) are commercially available or can be prepared by processesdescribed in the literature. Moreover, a substrate of the generalformula (III) where B═Cl can be prepared from the corresponding acid(B═OH) by chlorination using processes known from the literature (forexample Tetrahedron 2005, 61, 10827-10852, and the literature citedtherein).

A compound of the general formula (I) where Y═O can be synthesized by acoupling reaction of a compound of the corresponding general formula(II) with a substrate of the general formula (III) where B═Cl, ifappropriate in the presence of an acid scavenger/a base.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene) andnitriles (for example acetonitrile), or the reaction can be carried outin mixtures of two or more of these solvents. The preferred solvents aretetrahydrofuran and dichloromethane.

At least one equivalent of an acid scavenger/a base (for example Hünigbase, triethylamine or commercially available polymeric acid scavengers)is employed, based on the starting material of the general formula (II).If the starting material is a salt, at least two equivalents of the acidscavenger are required.

The reaction is usually carried out at temperatures of 0° C.-100° C. andpreferably at 20° C.-30° C., but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a couple of minutes and 48 hours.

After the reaction has ended, the compounds (I) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

Alternatively, a compound of the formula (I) where Y═O can also besynthesized from the corresponding compound of the general formula (II)using a substrate of the general formula (III) where B═OH in thepresence of a coupling agent, analogously to the procedures described inthe literature (for example Tetrahedron 2005, 61, 10827-10852, and thereferences cited therein).

Suitable coupling agents are, for example, peptide coupling agents (forexample, 1-ethyl-3-(30-dimethylamino)carbodiimide mixed with4-dimethylaminopyridine, 1-ethyl-3-(30-dimethylamino)carbodiimide mixedwith hydroxybenzotriazole, bromotri(pyrrolidino)phosphoniumhexafluorophosphate,2-(1H-7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyluroniumhexafluorophosphate methanaminium, etc.)

If appropriate, a base, such as for example, triethylamine or Hünigbase, may be employed in the reaction.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),nitriles (for example acetonitrile) and amides (for exampleN,N-dimethylformamide, N,N-dimethylacetamide), or the reaction can becarried out in mixtures of two or more of these solvents. The preferredsolvents are N,N-dimethylformamide and dichloromethane.

The reaction is usually carried out at temperatures of 0° C.-100° C. andpreferably at 0° C.-30° C., but it can also be carried out at the refluxtemperature of the reaction mixture. The reaction time varies dependingon the scale of the reaction and the reaction temperature, but isgenerally between a couple of minutes and 48 hours.

After the reaction has ended, the compounds (I) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

One way of preparing compounds of the formula (I) in which Y=sulphurfrom corresponding compounds (I) in which Y is oxygen is shown in Scheme14.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),nitriles (for example acetonitrile), carboxylic esters (for exampleethyl acetate) and amides (for example N,N-dimethylformamide,N,N-dimethylacetamide), or the reaction can be carried out in mixturesof two or more of these solvents. The preferred solvents are chloroformand 1,2-dimethoxyethane.

Suitable sulphurizing agents are, for example, Lawesson's reagent (s.Tetrahedron 1986, 42, 6555-6564, Tetrahedron Lett. 1993, 46, 7459-7462)and phosphorus pentasulphide. The starting material and the sulphurizingagent are employed in equimolar amounts; however, the sulphurizing agentmay, if appropriate, also be employed in excess.

The reaction is usually carried out at temperatures of 0° C.-150° C. andpreferably at 0° C.-100° C., but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a couple of minutes and 48 hours.

After the reaction has ended, the compounds (I) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography.

Novel are compounds of the formula (IX) in which

the symbols have the meanings below

PG represents unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl,C₁-C₄-alkoxycarbonyl or benzyloxycarbonyl,

-   R⁹═C₁-C₄-alkyl, C₃-C₆-cycloalkyl,

W, X and R² have the general, preferred, particularly preferred or veryparticularly preferred meanings given above.

Novel are compounds of the formula (X) in which

the symbols have the meanings below:PG represents unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl,C₁-C₄-alkoxycarbonyl or benzyloxycarbonyl,W, X and R² have the general, preferred, particularly preferred or veryparticularly preferred meanings given above.

Novel are compounds of the formula (XI) in which

the symbols have the meanings below

PG represents unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl,C₁-C₄-alkoxycarbonyl or benzyloxycarbonyl,

-   R¹⁰, R¹¹ and R¹²═C₁-C₄ alkyl or phenyl,-   W, X and R² have the general, preferred, particularly preferred or    very particularly preferred meanings given above.

Novel are compounds of the formula (IV) in which

the symbols have the meanings belowPG represents unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl,C₁-C₄-alkoxycarbonyl or benzyloxycarbonyl,

-   W, X, L², L³, R², R³, R⁸ and R⁹ have the general, preferred,    particularly preferred or very particularly preferred meanings given    above.

Novel are compounds of the formula (IIb) and (IIc) in which

the symbols have the meanings below

-   L² represents —CR⁹═CR⁹— for compounds of the formula (IIb)-   L² represents —C≡C— for compounds of the formula (IIc)-   W, X, L³, R², R³, and R⁹ have the general, preferred, particularly    preferred or very particularly preferred meanings given above.

Novel are compounds of the formula (XIII) in which

the symbols have the meanings belowA, W, X, Y and R² have the general, preferred, particularly preferred orvery particularly preferred meanings given above.

Novel are compounds of the formula (XIV) in which

the symbols have the meanings belowR¹⁰, R¹¹ and R¹²═C₁-C₄ alkyl or phenyl,A, W, X, Y, L¹ and R² have the general, preferred, particularlypreferred or very particularly preferred meanings given above.

The processes according to the invention for preparing the compounds ofthe formula (I) are preferably carried out using one or more reactionauxiliaries.

Suitable reaction auxiliaries are, if appropriate, the customaryinorganic or organic bases or acid acceptors. These preferably includealkali metal or alkaline earth metal acetates, amides, carbonates,bicarbonates, hydrides, hydroxides or alkoxides, such as for example,sodium acetate, potassium acetate or calcium acetate, lithium amide,sodium amide, potassium amide or calcium amide, sodium carbonate,potassium carbonate or calcium carbonate, sodium bicarbonate, potassiumbicarbonate or calcium bicarbonate, lithium hydride, sodium hydride,potassium hydride or calcium hydride, lithium hydroxide, sodiumhydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide,ethoxide, n- or isopropoxide, n-, iso-, s- or t-butoxide, or potassiummethoxide, ethoxide, n- or isopropoxide, n-, iso-, s- or t-butoxide,furthermore also basic organic nitrogen compounds, such as, for example,trimethylamine, triethylamine, tripropylamine, tributylamine,ethyldiisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine,ethyldicyclohexylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine,pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-,3,4-dimethyl- and 3,5-dimethylpyridine, 5-ethyl-2-methylpyridine,4-dimethylaminopyridine, N-methylpiperidine,1,4-diazabicyclo[2.2.2]-octane (DABCO),1,5-diazabicyclo[4.3.0]-non-5-ene (DBN), or1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).

The processes according to the invention are preferably carried outusing one or more diluents. Suitable diluents are virtually all inertorganic solvents. These preferably include aliphatic and aromatic,optionally halogenated hydrocarbons, such as pentane, hexane, heptane,cyclohexane, petroleum ether, benzine, ligroine, benzene, toluene,xylene, methylene chloride, ethylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorbenzene, ethers, such asdiethyl ether and dibutyl ether, glycol dimethyl ether and diglycoldimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone,methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone,esters, such as methyl acetate or ethyl acetate, nitriles, such as, forexample acetonitrile or propionitrile, amides, such as, for example,dimethylformamide, dimethylacetamid and N-methylpyrrolidone, and alsodimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphorictriamide and DMPU.

In the processes according to the invention, the reaction temperaturescan be varied within a relatively wide range. In general, the processesare carried out at temperatures between 0° C. and 250° C., preferably attemperatures between 10° C. and 185° C.

The processes according to the invention are generally carried out underatmospheric pressure. However, it is also possible to operate underelevated or reduced pressure.

To carry out the processes according to the invention, the startingmaterials required in each case are generally employed in approximatelyequimolar amounts. However, it is also possible to use a relativelylarge excess of in each case one of the components used. Work-up in theprocesses according to the invention is in each case carried out bycustomary methods (cf. the Preparation Examples).

The invention furthermore provides the non-medicinal use of theheterocyclyl-substituted thiazoles according to the invention forcontrolling unwanted microorganisms.

The invention furthermore relates to a composition for controllingunwanted microorganisms which comprises at least oneheterocyclyl-substituted thiazole according to the present invention.

Moreover, the invention relates to a method for controlling unwantedmicroorganisms, characterized in that the heterocyclyl-substitutedthiazoles according to the invention are applied to the microorganismsand/or in their habitat.

The invention furthermore relates to a seed treated with at least oneheterocyclyl-substituted thiazole according to the invention.

A last subject-matter of the invention relates to a method forprotecting seed against unwanted microorganisms by using seed treatedwith at least one heterocyclyl-substituted thiazole according to thepresent invention.

The compounds according to the invention have strong microbicidal actionand can be used for controlling unwanted microorganisms, such as fungiand bacteria, in crop protection and in the protection of materials.

The heterocyclyl-substituted thiazoles of the formula (I) according tothe invention have very good fungicidal properties and can be used incrop protection, for example, for controlling Plasmodiophoromycetes,Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetesand Deuteromycetes.

In crop protection, bactericides can be used for controlling, forexample, Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae,Corynebacteriaceae and Streptomycetaceae.

The fungicidal compositions according to the invention can be used forthe curative or protective control of phytopathogenic fungi.Accordingly, the invention also relates to curative and protectivemethods for controlling phytopathogenic fungi using the active compoundsor compositions according to the invention, which are applied to theseed, the plant or plant parts, the fruit or the soil in which theplants grow.

The compositions according to the invention for controllingphytopathogenic fungi in crop protection comprise an effective, butnon-phytotoxic amount of the active compounds according to theinvention. “Effective, but non-phytotoxic amount” means an amount of thecomposition according to the invention which is sufficient to controlthe fungal disease of the plant in a satisfactory manner or to eradicatethe fungal disease completely, and which, at the same time, does notcause any significant symptoms of phytotoxicity. In general, thisapplication rate may vary within a relatively wide range. It depends ona plurality of factors, for example on the fungus to be controlled, theplant, the climatic conditions and the ingredients of the compositionsaccording to the invention.

According to the invention, it is possible to treat all plants and partsof plants. Plants are to be understood here as meaning all plants andplant populations, such as wanted and unwanted wild plants or cropplants (including naturally occurring crop plants). Crop plants can beplants which can be obtained by conventional breeding and optimizationmethods or by biotechnological and genetic engineering methods orcombinations of these methods, including the transgenic plants andincluding plant cultivars which can or cannot be protected by varietalproperty rights. Parts of plants are to be understood as meaning allabove-ground and below-ground parts and organs of the plants, such asshoot, leaf, flower and root, examples which may be mentioned beingleaves, needles, stems, trunks, flowers, fruit bodies, fruits and seedsand also roots, tubers and rhizomes. Plant parts also include harvestedmaterial and vegetative and generative propagation material, for exampleseedlings, tubers, rhizomes, cuttings and seeds.

The following plants may be mentioned as plants which can be treatedaccording to the invention: cotton, flax, grapevines, fruit, vegetables,such as Rosaceae sp. (for example pomaceous fruit, such as apples andpears, but also stone fruit, such as apricots, cherries, almonds andpeaches and soft fruit such as strawberries), Ribesioidae sp.,Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp.,Moraceae sp., Oleaceae sp., Actimidaceae sp., Lauraceae sp., Musaceaesp. (for example banana trees and plantations), Rubiaceae sp. (forexample coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (forexample lemons, oranges and grapefruit), Solanaceae sp. (for exampletomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce),Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp.(for example cucumbers), Alliaceae sp. (for example leek, onions),Papilionaceae sp. (for example peas); major crop plants, such Gramineaesp. (for example maize, lawn, cereals such as wheat, rye, rice, barley,oats, millet and triticale), Asteraceae sp. (for example sunflowers),Brassicaceae sp. (for example white cabbage, red cabbage, broccoli,cauliflowers, brussels sprouts, pak choi, kohlrabi, garden radish, andalso oilseed rape, mustard, horseradish and cress), Fabacae sp. (forexample beans, peanuts), Papilionaceae sp. (for example soya beans),Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for examplesugarbeet, fodderbeet, swiss chard, beetroot); crop plants andornamental plants in garden and forest; and also in each casegenetically modified varieties of these plants. Preferably, cerealplants are treated according to the invention.

Some pathogens of fungal diseases which can be treated according to theinvention may be mentioned by way of example, but not by way oflimitation:

Diseases caused by powdery mildew pathogens, such as, for example,Blumeria species, such as, for example, Blumeria graminis; Podosphaeraspecies, such as, for example, Podosphaera leucotricha; Sphaerothecaspecies, such as, for example, Sphaerotheca fuliginea; Uncinula species,such as, for example, Uncinula necator;Diseases caused by rust disease pathogens, such as, for example,Gymnosporangium species, such as, for example, Gymnosporangium sabinae;Hemileia species, such as, for example, Hemileia vastatrix; Phakopsoraspecies, such as, for example, Phakopsora pachyrhizi and Phakopsorameibomiae; Puccinia species, such as, for example, Puccinia recondita,Puccinia graminis or Puccinia striformis; Uromyces species, such as, forexample, Uromyces appendiculatus;Diseases caused by pathogens from the group of the Oomycetes, such as,for example, Albugo species such as, for example, Albugo cundida, Bremiaspecies, such as, for example, Bremia lactucae; Peronospora species,such as, for example, Peronospora pisi or P. brassicae; Phytophthoraspecies, such as, for example Phytophthora infestans; Plasmoparaspecies, such as, for example, Plasmopara viticola; Pseudoperonosporaspecies, such as, for example, Pseudoperonospora humuli orPseudoperonospora cubensis; Pythium species, such as, for example,Pythium ultimum;Leaf blotch diseases and leaf wilt diseases caused, for example, byAlternaria species, such as, for example, Alternaria solani; Cercosporaspecies, such as, for example, Cercospora beticola; Cladiosporiumspecies, such as, for example, Cladiosporium cucumerinum; Cochliobolusspecies, such as, for example, Cochliobolus sativus (conidia form:Drechslera, Syn: Helminthosporium) or Cochliobolw miyabeanus;Colletotrichum species, such as, for example, Colletotrichumlindemuthanium; Cycloconium species, such as, for example, Cycloconiumoleaginum; Diaporthe species, such as, for example, Diaporthe citri;Elsinoe species, such as, for example, Elsinoe fawcettii; Gloeosporiumspecies, such as, for example, Gloeosporium laeticolor; Glomerellaspecies, such as, for example, Glomerella cingulata; Guignardia species,such as, for example, Guignardia bidwelli; Leptosphaeria species, suchas, for example, Leptosphaeria maculans; Magnaporthe species, such as,for example, Magnaporthe grisea; Microdochium species, such as, forexample, Microdochium nivale; Mycosphaerella species, such as, forexample, Mycosphaerella graminicola, Mycosphaerella arachidicola orMycosphaerella fijiensis; Phaeosphaeria species, such as, for example,Phaeosphaeria nodorum; Pyrenophora species, such as, for example,Pyrenophora teres or Pyrenophora tritici repentis; Ramularia species,such as, for example, Ramularia collo-cygni or Ramulania areola;Rhynchosporium species, such as, for example, Rhynchosporium secalis;Septoria species, such as, for example, Septoria apii or Septorialycopersici; Stagonospora species, such as, for example, Stagonosporanodorum; Typhula species, such as, for example, Typhula incarnata;Venturia species, such as, for example, Venturia inaequalis;Root and stem diseases caused, for example, by Corticium species, suchas, for example, Corticium graminearum; Fusarium species, such as, forexample, Fusarium oxysporum; Gaeumannomyces species, such as, forexample, Gaeumannomyces graminis; Plasmodiophora species, such as, forexample, Plasmodiophora brassicae; Rhizoctonia species, such as, forexample Rhizoctonia solani; Sarocladium species, such as, for example,Sarocladium oryzae; Sclerotium species, such as, for example, Sclerotiumoryzae; Tapesia species, such as, for example, Tapesia acuformis;Thielaviopsis species, such as, for example, Thielaviopsis basicola;Ear and panicle diseases (including maize cobs) caused, for example, byAlternaria species, such as, for example, Alternaria spp.; Aspergillusspecies, such as, for example, Aspergillus flavus; Cladosporium species,such as, for example, Cladosporium cladosporioides; Claviceps species,such as, for example, Claviceps purpurea; Fusarium species, such as, forexample, Fusarium culmorum; Gibberella species, such as, for example,Gibberella zeae; Monographella species, such as, for example,Monographella nivalis; Stagonospora species, such as for example,Stagonospora nodorum;Diseases caused by smut fungi, such as, for example, Sphacelothecaspecies, such as, for example, Sphacelotheca reiliana; Tilletia species,such as, for example, Tilletia caries or Tilletia controversa; Urocystisspecies, such as, for example, Urocystis occulta; Ustilago species, suchas, for example, Ustilago nuda;Fruit rot caused, for example, by Aspergillus species, such as, forexample, Aspergillus flavus; Botrytis species, such as, for example,Botrytis cinerea; Penicillium species, such as, for example, Penicilliumexpansum or Penicillium purpurogenum; Rhizopus species, such as, forexample, Rhizopus stolonifer; Sclerotinia species, such as, for example,Sclerotinia sclerotiorum; Verticilium species, such as, for example,Verticilium alboatrum;Seed- and soil-borne rot and wilt diseases, and also diseases ofseedlings, caused, for example, by Alternaria species, such as, forexample, Alternaria brassicicola; Aphanomyces species, such as, forexample, Aphanomyces euteiches; Ascochyta species, such as, for example,Ascochyta lentis; Aspergillus species, such as, for example, Aspergillusflavus; Cladosporium species, such as, for example, Cladosporiumherbarum; Cochliobolus species, such as, for example, Cochliobolussativus (conidia form: Drechslera, Bipolaris syn: Helminthosporium);Colletotrichum species, such as, for example, Colletotrichum coccodes;Fusarium species, such as, for example, Fusarium culmorum; Gibberellaspecies, such as, for example, Gibberella zeae; Macrophomina species,such as, for example, Macrophomina phaseolina; Microdochium species,such as, for example, Microdochium nivale; Monographella species, suchas, for example, Monographella nivalis; Penicillium species, such as,for example, Penicillium expansum; Phoma species, such as, for example,Phoma lingam; Phomopsis species, such as, for example, Phomopsis sojae;Phytophthora species, such as, for example, Phytophthora cactorum;Pyrenophora species, such as, for example, Pyrenophora graminea;Pyricularia species, such as, for example, Pyricularia oryzae; Pythiumspecies, such as, for example, Pythium ultimum; Rhizoctonia species,such as, for example, Rhizoctonia solani; Rhizopus species, such as, forexample, Rhizopus oryzae; Sclerotium species, such as, for example,Sclerotium rolfsii; Septoria species, such as, for example, Septorianodorum; Typhula species, such as, for example, Typhula incarnata;Verticillium species, such as, for example, Verticillium dahliae;Cancerous diseases, galls and witches' broom caused, for example, byNectria species, such as, for example, Nectria galligena;Wilt diseases caused, for example, by Monilinia species, such as, forexample, Monilinia laxa;Deformations of leaves, flowers and fruits caused, for example, byExobasidium species, such as, for example, Exobasidium vexams; Taphrinaspecies, such as, for example, Taphrina deformans;Degenerative diseases of woody plants caused, for example, by Escaspecies, such as, for example, Phaeomoniella chlamydospora,Phaeoacremonium aleophilum or Fomitiporia mediterranea; Ganodermaspecies, such as, for example, Ganoderma boninense;Diseases of flowers and seeds caused, for example, by Botrytis species,such as, for example, Botrytis cinerea;Diseases of plant tubers caused, for example, by Rhizoctonia species,such as, for example, Rhizoctonia solani; Helminthosporium species, suchas, for example, Helminthosporium solani;Diseases caused by bacterial pathogens, such as, for example,Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae; Pseudomonas species, such as, for example, Pseudomonas syringaepv. lachrymans; Erwinia species, such as, for example, Erwiniaamylovora.

Preference is given to controlling the following diseases of soya beans:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byalternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthephaseolorum), stem canker (Diaporthe phaseolorum var. caulivora),phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophoragregata), pythium rot (Pythium aphanidermatum, Pythium irregulare,Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctoniaroot rot, stem decay, and damping-off (Rhizoctonia solani), sclerotiniastem decay (Sclerotinia sclerotiorum), sclerotinia southern blight(Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

The active compounds according to the invention also show a stronginvigorating action in plants. Accordingly, they are suitable formobilizing the internal defenses of the plant against attack by unwantedmicroorganisms.

In the present context, plant-invigorating (resistance-inducing)substances are to be understood as meaning substances which are capableof stimulating the defense system of plants such that, when the treatedplants are subsequently inoculated with unwanted microorganisms, theydisplay substantial resistance to these microorganisms.

In the present case, undesired microorganisms are understood as meaningphytopathogenic fungi and bacteria. Thus, the substances according tothe invention can be employed for protecting plants against attack bythe abovementioned pathogens within a certain period of time after thetreatment. The period of time within which their protection is effectedis generally extended from 1 to 10 days, preferably 1 to 7 days, afterthe plants have been treated with the active compounds.

The fact that the active compounds, at the concentrations required forthe controlling of plant diseases, are well tolerated by plants permitsthe treatment of above-ground plant parts, of vegetative propagationmaterial and seed, and of the soil.

In this context, the active compounds according to the invention can beemployed particularly successfully for controlling diseases inviticulture and in the cultivation of fruit, potatoes and vegetables,such as, for example, in particular against powdery mildew fungi,Oomycetes, such as, for example, Phytophthora, Plasmopara,Pseudoperonospora and Pythium species.

The active compounds according to the invention are also suitable forincreasing the yield. Moreover, they display a low degree of toxicityand are well tolerated by plants.

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides,safeners, growth regulators or agents to improve plant properties, or asmicrobicides, for example as fungicides, antimycotics, bactericides,viricides (including agents against viroids) or as agents against MLO(Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). Ifappropriate, they can also be employed as insecticides. If appropriate,they can also be employed as intermediates or precursors for thesynthesis of other active compounds.

The active compounds according to the invention, in combination withgood plant tolerance and favourable toxicity to warm-blooded animals andbeing tolerated well by the environment, are suitable for protectingplants and plant organs, for increasing harvest yields and for improvingthe quality of harvested material in agriculture, in horticulture, inanimal husbandry, in forests, in gardens and leisure facilities, in theprotection of stored products and of materials, and in the hygienesector. They are preferably employed as crop protection agents. They areactive against normally sensitive and resistant species and against allor some stages of development.

The treatment according to the invention of the plants and plant partswith the active compounds or compositions is carried out directly or byaction on their surroundings, habitat or storage space using customarytreatment methods, for example by dipping, spraying, atomizing,irrigating, evaporating, dusting, fogging, broadcasting, foaming,painting, spreading-on, watering (drenching), drip irrigating and, inthe case of propagation material, in particular in the case of seeds,furthermore as a powder for dry seed treatment, a solution for wet seedtreatment, a water-soluble powder for slurry treatment, by encrusting,by coating with one or more coats, etc. It is furthermore possible toapply the active compounds by the ultra-low-volume method or to injectthe active compound preparation or the active compound itself into thesoil.

In the protection of materials, the compositions or active compoundsaccording to the invention can furthermore be employed for protectingindustrial materials against attack and destruction by unwantedmicroorganisms, such as, for example, fungi.

In the present context, industrial materials are understood as meaningnonliving materials which have been made for use in technology. Forexample, industrial materials which are to be protected by activecompounds according to the invention from microbial modification ordestruction can be glues, sizes, paper and board, textiles, leather,timber, paints and plastic articles, cooling lubricants and othermaterials which are capable of being attacked or destroyed bymicroorganisms. Parts of production plants, for example cooling-watercircuits, which can be adversely affected by the multiplication ofmicroorganisms may also be mentioned within the materials to beprotected. Industrial materials which may be mentioned with preferencefor the purposes of the present invention are glues, sizes, paper andboard, leather, timber, paints, cooling lubricants and heat-transferfluids, especially preferably timber. The compositions or activecompounds according to the invention can prevent disadvantageous effectssuch as rotting, decay, discoloration, decoloration or the formation ofmould.

The method according to the invention for controlling unwanted fungi canalso be employed for protecting storage goods. Here, storage goods areto be understood as meaning natural substances of vegetable or animalorigin or process products thereof of natural origin, for whichlong-term protection is desired. Storage goods of vegetable origin, suchas, for example, plants or plant parts, such as stems, leaves, tubers,seeds, fruits, grains, can be protected freshly harvested or afterprocessing by (pre)drying, moistening, comminuting, grinding, pressingor roasting. Storage goods also include timber, both unprocessed, suchas construction timber, electricity poles and barriers, or in the formof finished products, such as furniture. Storage goods of animal originare, for example, hides, leather, furs and hairs. The active compoundsaccording to the invention can prevent disadvantageous effects, such asrotting, decay, discoloration, decoloration or the formation of mould.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular moulds, wood-discoloring andwood-destroying fungi (Basidiomycetes) and against slime organisms andalgae. Microorganisms of the following genera may be mentioned asexamples: Alternaria, such as Alternaria tenuis; Aspergillus, such asAspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora,such as Coniophora puetana; Lentinus, such as Lentinus tigrinus;Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporusversicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma,such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride;Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonasaeruginosa; Staphylococcus, such as Staphylococcus aureus.

The present invention furthermore relates to a composition forcontrolling unwanted microorganisms comprising at least one of theheteracyclyl-substituted thiazoles according to the invention. These arepreferably fungicidal compositions comprising auxiliaries, solvents,carriers, surfactants or extenders suitable for use in agriculture.

According to the invention, a carrier is a natural or synthetic, organicor inorganic substance with which the active compounds are mixed orbonded for better applicability, in particular for application to plantsor parts of plants or seed. The carrier, which may be solid or liquid,is generally inert and should be suitable for use in agriculture.

Suitable solid carriers are: for example ammonium salts and groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and silicates; suitablesolid carriers for granules are:

for example crushed and fractionated natural rocks, such as calcite,marble, pumice, sepiolite and dolomite, and also synthetic granules ofinorganic and organic meals, and granules of organic material, such aspaper, sawdust, coconut shells, maize cobs and tobacco stalks; suitableemulsifiers and/or foam-formers are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates and also proteinhydrolysates; suitable dispersants are nonionic and/or ionic substances,for example from the classes of the alcohol/POE and/or POP ethers, acidand/or POP/POE esters, alkylaryl and/or POP/POE ethers, fat and/orPOP/POE adducts, POE and/or POP polyol derivatives, POE and/orPOP/sorbitan or sugar adducts, alkyl or aryl sulphates, sulphonates andphosphates, or the corresponding PO ether adducts. Furthermore suitableoligo- or polymers, for example those derived from vinylic monomers,from acrylic acid, from EO and/or PO alone or in combination with, forexample, (poly)alcohols or (poly)amines. It is also possible to employlignin and its sulphonic acid derivatives, unmodified and modifiedcelluloses, aromatic and/or aliphatic sulphonic acids and their adductswith formaldehyde.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, water- and oil-basedsuspensions, powders, dusts, pastes, soluble powders, soluble granules,granules for broadcasting, suspension-emulsion concentrates, naturalmaterials impregnated with active compound, synthetic materialsimpregnated with active compound, fertilizers and alsomicroencapsulations in polymeric substances.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsions, water- or oil-based suspensions, powders, wettablepowders, pastes, soluble powders, dusts, soluble granules, granules forbroadcasting, suspension-emulsion concentrates, natural materialsimpregnated with active compound, synthetic materials impregnated withactive compound, fertilizers and also microencapsulations in polymericsubstances. Application is carried out in a customary manner, forexample by pouring, spraying, atomizing, broadcasting, dusting, foaming,painting-on, etc. It is furthermore possible to apply the activecompounds by the ultra-low-volume method or to inject the preparation ofactive compound or the active compound itself into the soil. It is alsopossible to treat the seed of the plants.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one customaryextender, solvent or diluent, emulsifier, dispersant and/or binder orfixative, wetting agent, water repellant, if appropriate siccatives andUV stabilizers and if appropriate colorants and pigments, antifoams,preservatives, secondary thickeners, glues, gibberellins and otherprocessing auxiliaries.

The compositions according to the invention include not onlyformulations which are already ready to use and can be applied to theplant or the seed using a suitable apparatus, but also commercialconcentrates which have to be diluted with water prior to use.

The active compounds according to the invention can be present as suchor in their (commercial) formulations and also in the use forms preparedfrom these formulations as a mixture with other (known) activecompounds, such as insecticides, attractants, sterilants, bactericides,acaricides, nematicides, fungicides, growth regulators, herbicides,fertilizers, safeners and/or semiochemicals.

Suitable for use as auxiliaries are substances which are suitable forimparting to the composition itself and/or to preparations derivedtherefrom (for example spray liquors, seed dressings) particularproperties such as certain technical properties and/or also particularbiological properties. Typical suitable auxiliaries are: extenders,solvents and carriers.

Suitable extenders are, for example, water, polar and nonpolar organicchemical liquids, for example from the classes of the aromatic andnon-aromatic hydrocarbons (such as paraffins, alkylbenzenes,alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, ifappropriate, may also be substituted, etherified and/or esterified), theketones (such as acetone, cyclohexanone), esters (including fats andoils) and (poly)ethers, the unsubstituted and substituted amines,amides, lactams (such as N-alkylpyrrolidones) and lactones, thesulphones and sulphoxides (such as dimethyl sulphoxide).

Liquefied gaseous extenders or carriers are liquids which are gaseous atambient temperature and under atmospheric pressure, for example aerosolpropellants, such as halogenated hydrocarbons, and also butane, propane,nitrogen and carbon dioxide.

Tackifiers, such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules and latices, such as gumarabic, polyvinyl alcohol, polyvinyl acetate, or else naturalphospholipids, such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

If the extender used is water, it is also possible to use, for example,organic solvents as auxiliary solvents. Suitable liquid solvents areessentially: aromatic compounds, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatic compounds or chlorinatedaliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes ormethylene chloride, aliphatic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, alcohols, such as butanolor glycol, and also ethers and esters thereof, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, stronglypolar solvents, such as dimethylformamide and dimethyl sulphoxide, andalso water.

The compositions according to the invention may additionally comprisefurther components, such as, for example, surfactants. Suitablesurfactants are emulsifiers and/or foam-formers, dispersants or wettingagents having ionic or nonionic properties, or mixtures of thesesurfactants. Examples of these are salts of polyacrylic acid, salts oflignosulphonic acid, salts of phenolsulphonic acid ornaphthalenesulphonic acid, polycondensates of ethylene oxide with fattyalcohols or with fatty acids or with fatty amines, substituted phenols(preferably alkylphenols or arylphenols), salts of sulphosuccinicesters, taurine derivatives (preferably alkyl taurates), phosphoricesters of polyethoxylated alcohols or phenols, fatty esters of polyols,and derivatives of the compounds containing sulphates, sulphonates andphosphates, for example alkylaryl polyglycol ethers, alkylsulphonates,alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphitewaste liquors and methylcellulose. The presence of a surfactant isrequired if one of the active compounds and/or one of the inert carriersis insoluble in water and the application is carried out in water. Theproportion of surfactants is between 5 and 40 percent by weight of thecompositions according to the invention.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide, Prussian blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients, such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

Other possible additives are perfumes, mineral or vegetable oils, ifappropriate modified, waxes and nutrients (including trace nutrients),such as salts of iron, manganese, boron, copper, cobalt, molybdenum andzinc.

Stabilizers, such as low-temperature stabilizers, preservatives,antioxidants, light stabilizers or other agents which improve chemicaland/or physical stability may also be present.

If appropriate, it is also possible for other additional components tobe present, for example protective colloids, binders, glues, thickeners,thixotropic agents, penetrants, stabilizers, sequestrants, complexfoamers. In general, the active compounds can be combined with any solidor liquid additive customarily used for formulation purposes.

The formulations generally comprise between 0.05 and 99% by weight, 0.01and 98% by weight, preferably between 0.1 and 95% by weight,particularly preferably between 0.5 and 90% by weight, of activecompound, very particularly preferably between 10 and 70 percent byweight.

The formulations described above can be employed in a method accordingto the invention for controlling unwanted microorganisms where theheterocyclyl-substituted thiazoles according to the invention areapplied to the microorganisms and/or their habitat.

The active compounds according to the invention, as such or in theirformulations, can also be used in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, for example tobroaden the activity spectrum or to prevent the development ofresistance.

Suitable mixing partners are, for example, known fungicides,insecticides, acaricides, nematicides or else bactericides (see alsoPesticide Manual, 13th ed.).

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, safeners and/or semiochemicals isalso possible.

Application is carried out in a manner adapted to the use forms.

The invention furthermore comprises a method for treating seed.

A further aspect of the present invention relates in particular to seedtreated with at least one of the heterocyclyl-substituted thiazolesaccording to the invention. The seed according to the invention is usedin methods for protecting seed against phytopathogenic harmful fungi. Inthese methods, seed treated with at least one active compound accordingto the invention is used.

The compositions and active compounds according to the invention arealso suitable for treating seed. A large part of the damage to cropplants which is caused by harmful organisms occurs when the seed isattacked during storage or after the seed is introduced into the soil,and also during and after germination of the plant. This phase isparticularly critical since the roots and shoots of the growing plantare particularly sensitive and even minor damage can lead to the deathof the whole plant. Protecting the seed and the germinating plant by theuse of suitable compositions is therefore of great interest.

The control of phytopathogenic harmful fungi by treating the seed ofplants has been known for a long time and is subject-matter ofcontinuous improvements. However, in the treatment of seed, a number ofproblems are encountered which can not always by resolved in asatisfactory manner. Thus, it is desirable to develop methods forprotecting the seed and the germinating plant which dispense with theadditional application of crop protection agents after sowing or afterthe emergence of the plants or where additional applications are atleast significantly reduced. It is furthermore desirable to optimize theamount of active compound employed in such a way as to provide maximumprotection for the seed and the germinating plant from attack byphytopathogenic fungi, but without damaging the plant itself by theactive compound employed. In particular, methods for the treatment ofseed should also take into consideration the intrinsic fungicidalproperties of transgenic plants in order to achieve optimum protectionof the seed and the germinating plant with a minimum of crop protectionagents being employed.

The present invention therefore also relates to a method for theprotection of seed and germinating plants from attack by animal pestsand/or phytopathogenic harmful fungi, by treating the seed with acomposition according to the invention. The invention likewise relatesto the use of the compositions according to the invention for thetreatment of seed for protecting the seed and the germinating plant fromphytopathogenic fungi. Furthermore, the invention relates to seed whichhas been treated with a composition according to the invention so as toafford protection from phytopathogenic fungi.

Animal pests and/or phytopathogenic harmful fungi which damage the plantafter emergence are primarily controlled by treating the soil and theabove-ground parts of the plants with crop protection agents. Owing toconcerns with a possible impact of the crop protection agents on theenvironment and human and animal health, there are efforts to reduce theamount of active compounds applied.

One of the advantages of the present invention is that the particularsystemic properties of the compositions according to the invention meanthat treatment of the seed with these compositions not only protects theseed itself, but also the resulting plants after emergence, from animalpests and/or phytopathogenic harmful fungi. In this manner, theimmediate treatment of the crop at the time of sowing or shortlythereafter can be dispensed with.

It is also to be considered advantageous that the compositions andactive compounds according to the invention can be used in particularalso for transgenic seed, where the plant growing from this seed iscapable of expressing a protein which acts against pests. By treatingsuch a seed with the compositions and active compounds according to theinvention, is possible to control certain pests even by the expressionof the, for example, insecticidal protein. Surprisingly, a furthersynergistic effect may be observed here, which further improves theeffectiveness of the protection against attack by pests.

The compositions according to the invention are suitable for protectingseed of any plant variety which is employed in agriculture, in thegreenhouse, in forests or in horticulture. In particular, this takes theform of seed of cereals (such as wheat, barley, rye, millet and oats),maize, cotton, soya beans, rice, potatoes, sunflowers, beans, coffee,beet (for example sugar beet and fodder beet), peanuts, vegetables (suchas tomatoes, cucumbers, onions and lettuce), lawns and ornamentalplants. The treatment of seed of cereals (such as wheat, barley, rye andoats), maize and rice is of particular importance.

As also described below, the treatment of transgenic seed with thecompositions or active compounds according to the invention is also ofparticular importance. This takes the form of seed of plants whichcomprise at least one heterologous gene which governs the expression ofa polypeptide or protein with insecticidal properties. The heterologousgene in transgenic seed may be derived, for example, from microorganismsof the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma,Clavibacter, Glomus or Gliocladium. This heterologous gene preferablyoriginates from Bacillus sp., the gene product having activity againstthe European corn borer and/or the Western corn root worm. It isparticularly preferably a heterologous gene derived from Bacillusthuringiensis.

In the context of the present invention, the composition according tothe invention is applied to the seed either alone or in a suitableformulation. Preferably, the seed is treated in a state which is stableenough to avoid damage during treatment. In general, the seed may betreated at any point in time between harvest and sowing. The seedusually used has been separated from the plant and freed from cobs,shells, stalks, coats, hairs or the flesh of the fruits. Thus, forexample, it is possible to use seed which has been harvested, cleanedand dried to a moisture content of below 15% by weight. Alternatively,it is also possible to use seed which, after drying, has, for example,been treated with water and then dried again.

When treating the seed, care must generally be taken that the amount ofthe composition according to the invention applied to the seed and/orthe amount of further additives is chosen in such a way that thegermination of the seed is not adversely affected, or that the resultingplant is not damaged. This must be borne in mind in particular in thecase of active compounds which may have phytotoxic effects at certainapplication rates.

The compositions according to the invention can be applied directly,that is to say without comprising further components and without havingbeen diluted. In general, it is preferable to apply the composition tothe seed in the form of a suitable formulation. Suitable formulationsand methods for the treatment of seed are known to the skilled workerand are described, for example, in the following documents: U.S. Pat.No. 4,272,417 A, U.S. Pat. No. 4,245,432 A, U.S. Pat. No. 4,808,430 A,U.S. Pat. No. 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO2002/028186 A2.

The active compound which can be used according to the invention can beconverted into customary seed dressing formulations, such as solutions,emulsions, suspensions, powders, foams, slurries or other coatingmaterials for seed, and also ULV formulations.

These formulations are prepared in a known manner by mixing the activecompounds or active compound combinations with customary additives, suchas, for example, customary extenders and also solvents or diluents,colorants, wetting agents, dispersants, emulsifiers, defoamers,preservatives, secondary thickeners, adhesives, gibberellins and alsowater.

Suitable colorants that may be present in the seed dressing formulationswhich can be used according to the invention include all colorantscustomary for such purposes. Use may be made both of pigments, ofsparing solubility in water, and of dyes, which are soluble in water.Examples that may be mentioned include the colorants known under thedesignations rhodamine B, C.I. Pigment Red 112, and C.I. Solvent Red 1.

Suitable wetting agents that may be present in the seed dressingformulations which can be used according to the invention include allsubstances which promote wetting and are customary in the formulation ofactive agrochemical compounds. With preference it is possible to usealkylnaphthalene-sulphonates, such as diisopropyl- ordiisobutylnaphthalene-sulphonates.

Suitable dispersants and/or emulsifiers that may be present in the seeddressing formulations which can be used according to the inventioninclude all nonionic, anionic, and cationic dispersants which arecustomary in the formulation of active agrochemical compounds. Withpreference, it is possible to use nonionic or anionic dispersants ormixtures of nonionic or anionic dispersants. Particularly suitablenonionic dispersants are ethylene oxide-propylene oxide block polymers,alkylphenol polyglycol ethers, and tristyrylphenol polyglycol ethers,and their phosphated or sulphated derivatives. Particularly suitableanionic dispersants are lignosulphonates, polyacrylic salts, andarylsulphonate-formaldehyde condensates.

Suitable defoamers that may be present in the seed dressing formulationswhich can be used according to the invention include all foam-inhibitingsubstances which are customary in the formulation of active agrochemicalcompounds. With preference it is possible to use silicone defoamers andmagnesium stearate.

Suitable preservatives that may be present in the seed dressingformulations which can be used according to the invention include allsubstances which can be used for such purposes in agrochemicalcompositions. By way of example, mention may be made of dichlorophen andbenzyl alcohol hemiformal.

Suitable secondary thickeners that may be present in the seed dressingformulations which can be used according to the invention include allsubstances which can be used for such purposes in agrochemicalcompositions. Preferred suitability is possessed by cellulosederivatives, acrylic acid derivatives, xanthan, modified clays, andfinely divided silica.

Suitable adhesives that may be present in the seed dressing formulationswhich can be used according to the invention include all customarybinders which can be used in seed dressing. With preference, mention maybe made of polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcoholand tylose.

Suitable gibberellins that may be present in the seed dressingformulations which can be used according to the invention are preferablythe gibberellins A1, A3 (=gibberellinic acid), A4 and A7; particularlypreferably, gibberellinic acid is used. The gibberellins are known (cf.R. Wegler “Chemie der Pflanzenschutz- and Schädlingsbekämpfungsmittel”,Vol. 2, Springer Verlag, 1970, pp. 401-412).

The seed dressing formulations which can be used according to theinvention may be used directly or after dilution with water beforehandto treat seed of any of a very wide variety of types. For instance, theconcentrates or the preparations obtainable therefrom by dilution withwater may be used to dress the seed of cereals, such as wheat, barley,rye, oats, and triticale, and also the seed of maize, rice, oilseedrape, peas, field beans, cotton, sunflowers, and beets, or elsevegetable seed of any of a very wide variety of kinds. The seed dressingformulations which can be used according to the invention or theirdilute preparations may also be used to dress seed of transgenic plants.In this context, additional synergistic effects may also arise ininteraction with the substances formed by expression.

Suitable mixing equipment for treating seed with the seed dressingformulations which can be used according to the invention or thepreparations prepared from them by adding water includes all mixingequipment which can commonly be used for dressing. The specificprocedure adopted when dressing comprises introducing the seed into amixer, adding the particular desired amount of seed dressingformulation, either as it is or following dilution with waterbeforehand, and carrying out mixing until the formulation is uniformlydistributed on the seed. Optionally, a drying operation follows.

The application rate of the seed dressing formulations which can be usedaccording to the invention may be varied within a relatively wide range.It depends on the respective content of the active compounds in theformulations and on the seed. In general, the application rates ofactive compound combination are between 0.001 and 50 g per kilogram ofseed, preferably between 0.01 and 15 g per kilogram of seed.

In addition, the compounds of the formula (I) according to the inventionalso have very good antimycotic activity. They have a very broadantimycotic activity spectrum in particular against dermatophytes andyeasts, moulds and diphasic fungi (for example against Candida speciessuch as Candida albicans, Candida glabrata) and Epidermophytonfloccosum, Aspergillus species such as Aspergillus niger and Aspergillusfumigatus, Trichophyton species such as Trichophyton mentagrophytes,Microsporon species such as Microsporon canis and audouinii. Theenumeration of these fungi does by no means limit the mycotic spectrumwhich can be covered, but is only for illustration.

Accordingly, the active compounds of the formula (I) according to theinvention can be used both in medical and in non-medical applications.

The active compounds can be applied as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. Application is carried out in a customary manner, forexample by watering, spraying, atomizing, broadcasting, dusting,foaming, painting-on, etc. It is also possible to apply the activecompounds by the ultra-low-volume method or to inject the preparation ofactive compound or the active compound itself into the soil. It is alsopossible to treat the seed of the plants.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the type of application. The application rate of theactive compounds according to the invention is

-   -   in the treatment of parts of plants, for example leaves: from        0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha,        particularly preferably from 50 to 300 g/ha (when the        application is by watering or dripping, it is possible to reduce        the application rate even more, in particular when inert        substrates such as rock wool or perlite are used);    -   in the treatment of seed: from 2 to 200 g per 100 kg of seed,        preferably from 3 to 150 g per 100 kg of seed, particularly        preferably from 2.5 to 25 g per 100 kg of seed, very        particularly preferably from 2.5 to 12.5 g per 100 kg of seed;    -   in soil treatment: from 0.1 to 10 000 g/ha, preferably from 1 to        5000 g/ha.

These application rates are mentioned only in an exemplary manner andare not limiting for the purpose of the invention.

In the veterinary sector and in animal keeping, the active compoundsaccording to the invention are applied in the known manner by enteraladministration in the form of, for example, tablets, capsules, drinks,drenches, granules, pastes, boluses, the feed-through method,suppositories, by parenteral administration, such as, for example, byinjections (intramuscular, subcutaneous, intravenous, intraperitonealand the like), implants, by nasal application, by dermal application inthe form of, for example, bathing or dipping, spraying, pouring-on andspotting-on, washing, dusting, and with the aid ofactive-compound-comprising shaped articles such as collars, ear tags,tail tags, limb bands, halters, marking devices and the like.

When used for livestock, poultry, domestic animals and the like, theactive compounds of the formula (I) can be applied as formulations (forexample powders, emulsions, flowables) which comprise the activecompounds in an amount of from 1 to 80% by weight, either directly orafter 100- to 10 000-fold dilution, or else as a chemical bath.

If appropriate, the ready-to-use compositions may comprise furtherinsecticides and, if appropriate, one or more further fungicides.

With respect to possible additional mixing partners, reference is madeto the insecticides and fungicides mentioned above.

The compounds according to the invention can also be used for protectingobjects which come into contact with salt water or brackish water, suchas hulls, screens, nets, buildings, moorings and signalling systems,against colonization.

The compounds according to the invention, alone or in combination withother active compounds, can furthermore be employed as antifoulingagents.

The treatment method according to the invention can be used for treatinggenetically modified organisms (GMOs), for example plants or seeds.Genetically modified plants (or transgenic plants) are plants in which aheterologous gene has been stably integrated into the genome. Theexpression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which is/are present in the plant (using for example,antisense technology, cosuppression technology or RNA interference(RNAi) technology. A heterologous gene that is located in the genome isalso called a transgene. A transgene that is defined by its particularlocation in the plant genome is called a transformation or transgenicevent.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, the following effects, whichexceed the effects which were actually to be expected, are possible:reduced application rates and/or a widening of the activity spectrumand/or an increase in the activity of the active compounds andcompositions which can be used according to the invention, better plantgrowth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, bigger fruits, larger plant height, greener leaf colour,earlier flowering, higher quality and/or a higher nutritional value ofthe harvested products, higher sugar concentration within the fruits,better storage stability and/or processability of the harvestedproducts.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are also suitable for mobilizing the defense system ofthe plant against attack by unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. This may, if appropriate, be one of thereasons for the enhanced activity of the combinations according to theinvention, for example against fungi. Plant-strengthening(resistance-inducing) substances are to be understood as meaning, in thepresent context, those substances or combinations of substances whichare capable of stimulating the defense system of plants in such a waythat, when subsequently inoculated with unwanted phytopathogenic fungiand/or microorganisms and/or viruses, the treated plants display asubstantial degree of resistance to these unwanted phytopathogenic fungiand/or microorganisms and/or viruses. In the present case, unwantedphytopathogenic fungi and/or microorganisms and/or viruses are to beunderstood as meaning phytopathogenic fungi, bacteria and viruses. Thus,the substances according to the invention can be employed for protectingplants against attack by the abovementioned pathogens within a certainperiod of time after the treatment. The period of time within whichprotection is effected generally extends from 1 to 10 days, preferably 1to 7 days, after the treatment of the plants with the active compounds.

Plants and plant cultivars which are preferably treated according to theinvention include all plants with genetic material which bestows uponthese plants particularly advantageous useful properties (whether thiswas achieved by breeding and/or biotechnology is immaterial).

Plants and plant cultivars which are also preferably treated accordingto the invention are resistant against one or more biotic stressfactors, i.e. said plants have a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstress factors. Abiotic stress conditions may include, for example,drought, cold temperature exposure, heat exposure, osmotic stress,flooding, increased soil salinity, increased mineral exposure, ozoneexposure, high light exposure, limited availability of nitrogennutrients, limited availability of phosphorus nutrients or shadeavoidance.

Plants and plant cultivars which may also be treated according to theinvention are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermoreby affected by improved plant architecture (under stress and non-stressconditions), including early flowering, flowering control for hybridseed production, seedling vigour, plant size, internode number anddistance, root growth, seed size, fruit size, pod size, pod or earnumber, seed number per pod or ear, seed mass, enhanced seed filling,reduced seed dispersal, reduced pod dehiscence and lodging resistance.Further yield traits include seed composition, such as carbohydratecontent, protein content, oil content and composition, nutritionalvalue, reduction in anti-nutritional compounds, improved processabilityand better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristic of heterosis or the hybrideffect which results in generally higher yield, vigour, health andresistance towards biotic and abiotic stress factors. Such plants aretypically made by crossing an inbred male sterile parent line (thefemale parent) with another inbred male fertile parent line (the maleparent). Hybrid seed is typically harvested from the male sterile plantsand sold to growers. Male sterile plants can sometimes (e.g. in corn) beproduced by detasseling, (i.e. the mechanical removal of the malereproductive organs or male flowers) but, more typically, male sterilityis the result of genetic determinants in the plant genome. In that case,and especially when seed is the desired product to be harvested from thehybrid plants, it is typically useful to ensure that male fertility inthe hybrid plants, which contain the genetic determinants responsiblefor male sterility, is fully restored. This can be accomplished byensuring that the male parents have appropriate fertility restorer geneswhich are capable of restoring the male fertility in hybrid plants thatcontain the genetic determinants responsible for male sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species. However, genetic determinants for male sterilitycan also be located in the nuclear genome. Male sterile plants can alsobe obtained by plant biotechnology methods such as genetic engineering.A particularly useful means of obtaining male sterile plants isdescribed in WO 89/10396 in which, for example, a ribonuclease such as abarnase is selectively expressed in the tapetum cells in the stamens.Fertility can then be restored by expression in the tapetum cells of aribonuclease inhibitor such as barstar.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.For example, glyphosate-tolerant plants can be obtained by transformingthe plant with a gene encoding the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium, the CP4 gene of the bacterium Agrobacterium sp., the genesencoding a petunia EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It canalso be a mutated EPSPS. Glyphosate-tolerant plants can also be obtainedby expressing a gene that encodes a glyphosate oxidoreductase enzyme.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyl transferase enzyme. Glyphosate-tolerantplants can also be obtained by selecting plants containingnaturally-occurring mutations of the above-mentioned genes.

Other herbicide-resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition. One such efficientdetoxifying enzyme is, for example, an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species). Plants expressing an exogenous phosphinothricinacetyltransferase have been described.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyse thereaction in which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD-inhibitors can be transformedwith a gene encoding a naturally-occurring resistant HPPD enzyme, or agene encoding a mutated HPPD enzyme. Tolerance to HPPD-inhibitors canalso be obtained by transforming plants with genes encoding certainenzymes enabling the formation of homogentisate despite the inhibitionof the native HPPD enzyme by the HPPD-inhibitor. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme prephenate dehydrogenase in addition to a geneencoding an HPPD-tolerant enzyme.

Still further herbicide-resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitorsinclude, for example, sulphonylurea, imidazolinone, triazolopyrimidines,pyrimidinyloxy(thio)benzoates, and/or sulphonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxy acid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides. The production ofsulphonylurea-tolerant plants and imidazolinone-tolerant plants has beendescribed in the international publication WO 1996/033270. Furthersulphonylurea- and imidazolinone-tolerant plants have also beendescribed, for example in WO 2007/024782.

Other plants tolerant to imidazolinone and/or sulphonylurea can beobtained by induced mutagenesis, by selection in cell cultures in thepresence of the herbicide or by mutation breeding.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

In the present context, the term “insect-resistant transgenic plant”includes any plant containing at least one transgene comprising a codingsequence encoding:

-   1) an insecticidal crystal protein from Bacillus thuringiensis or an    insecticidal portion thereof, such as the insecticidal crystal    proteins listed online at:    http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or    insecticidal portions thereof, for example proteins of the Cry    protein classes Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry3Ae or Cry3Bb or    insecticidal portions thereof; or-   2) a crystal protein from Bacillus thuringiensis or a portion    thereof which is insecticidal in the presence of a second other    crystal protein from Bacillus thuringiensis or a portion thereof,    such as the binary toxin made up of the Cy34 and Cy35 crystal    proteins; or-   3) a hybrid insecticidal protein comprising parts of two different    insecticidal crystal proteins from Bacillus thuringiensis, such as a    hybrid of the proteins of 1) above or a hybrid of the proteins of 2)    above, for example the Cry1A.105 protein produced by maize event    MON98034 (WO 2007/027777); or-   4) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes induced in the encoding DNA during cloning or    transformation, such as the Cry3Bbl protein in maize events MON863    or MON88017, or the Cry3A protein in maize event MIR604;-   5) an insecticidal secreted protein from Bacillus thuringiensis or    Bacillus cereus, or an insecticidal portion thereof, such as the    vegetative insecticidal proteins (VIP) listed at:    http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html, for    example proteins from the VIP3Aa protein class; or-   6) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a second secreted protein    from Bacillus thuringiensis or B. cereus, such as the binary toxin    made up of the VIP1a and VIP2A proteins;-   7) a hybrid insecticidal protein comprising parts from different    secreted proteins from Bacillus thuringiensis or Bacillus cereus,    such as a hybrid of the proteins in 1) above or a hybrid of the    proteins in 2) above; or-   8) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes induced in the encoding DNA during cloning or    transformation (while still encoding an insecticidal protein), such    as the VIP3Aa protein in cotton event COT102.

Of course, insect-resistant transgenic plants, as used herein, alsoinclude any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected or to delay insect resistance developmentto the plants, by using different proteins insecticidal to the sametarget insect species but having a different mode of action, such asbinding to different receptor binding sites in the insect.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

-   a. plants which contain a transgene capable of reducing the    expression and/or the activity of the poly(ADP-ribose)polymerase    (PARP) gene in the plant cells or plants.-   b. plants which contain a stress tolerance-enhancing transgene    capable of reducing the expression and/or the activity of the PARG    encoding genes of the plants or plant cells;-   c. plants which contain a stress tolerance-enhancing transgene    coding for a plant-functional enzyme of the nicotinamide adenine    dinucleotide salvage biosynthesis pathway, including nicotinamidase,    nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide    adenyl transferase, nicotinamide adenine dinucleotide synthetase or    nicotinamide phosphoribosyltransferase.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as, for example:

-   1) transgenic plants which synthesize a modified starch, which in    its physical-chemical characteristics, in particular the amylose    content or the amylose/amylopectin ratio, the degree of branching,    the average chain length, the side chain distribution, the viscosity    behaviour, the gelling strength, the starch grain size and/or the    starch grain morphology, is changed in comparison with the    synthesized starch in wild type plant cells or plants, so that this    modified starch is better suited for special applications.-   2) transgenic plants which synthesize non-starch carbohydrate    polymers or which synthesize non-starch carbohydrate polymers with    altered properties in comparison to wild type plants without genetic    modification. Examples are plants which produce polyfructose,    especially of the inulin and levan type, plants which produce    alpha-1,4-glucans, plants which produce alpha-1,6 branched    alpha-1,4-glucans, and plants producing alternan.-   3) transgenic plants which produce hyaluronan.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as cotton plants, with altered fibrecharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants containing a mutation imparting such alteredfibre characteristics and include:

-   a) plants, such as cotton plants, which contain an altered form of    cellulose synthase genes,-   b) plants, such as cotton plants, which contain an altered form of    rsw2 or rsw3 homologous nucleic acids;-   c) plants, such as cotton plants, with an increased expression of    sucrose phosphate synthase;-   d) plants, such as cotton plants, with an increased expression of    sucrose synthase;-   e) plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the basis of the fibre cell is altered, for    example through downregulation of fibre-selective β-1,3-glucanase;-   f) plants, such as cotton plants, which have fibres with altered    reactivity, for example through the expression of the    N-acetylglucosaminetransferase gene including nodC and chitin    synthase genes.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation or by selection of plants containinga mutation imparting such altered oil characteristics and include:

-   a) plants, such as oilseed rape plants, which produce oil having a    high oleic acid content;-   b) plants, such as oilseed rape plants, which produce oil having a    low linolenic acid content;-   c) plants, such as oilseed rape plants, which produce oil having a    low level of saturated fatty acids.

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins, are the following which are sold under the tradenames: YIELD GARD® (for example maize, cotton, soya beans), KnockOut®(for example maize), BiteGard® (for example maize), Bt-Xtra® (forexample maize), StarLink® (for example maize), Bollgard® (cotton),Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (for example maize),Protecta® and NewLeaf® (potato). Examples of herbicide-tolerant plantswhich may be mentioned are maize varieties, cotton varieties and soyabean varieties which are sold under the trade names: Roundup Ready®(tolerance to glyphosate, for example maize, cotton, soya beans),Liberty Link® (tolerance to phosphinothricin, for example oilseed rape),IMF® (tolerance to imidazolinone) and SCS® (tolerance to sulphonylurea,for example maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, or acombination of transformation events, that are listed for example in thedatabases for various national or regional regulatory agencies (see forexample http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

According to the invention, the plants listed can be treatedparticularly advantageously with the compounds of the general formula(I) or the active compound mixtures according to the invention. Thepreferred ranges indicated above for the active compounds and mixturesalso apply to the treatment of these plants. Particular emphasis isgiven to treating the plants with the compounds and mixturesspecifically indicated in the present text.

The compositions or active compounds according to the invention can alsobe used to protect plants for a certain period after treatment againstattack by the pathogens mentioned. The period for which protection isprovided generally extends over 1 to 28 days, preferably over 1 to 14days, particularly preferably over 1 to 10 days, very particularlypreferably over 1 to 7 days, after the treatment of the plants with theactive compounds, or over up to 200 days after seed treatment.

Preparation and use of the active compounds of the formula (I) accordingto the invention is shown in the examples below. However, the inventionis not limited to these examples.

General remarks: Unless indicated otherwise, all chromatographicpurification and separation steps were carried out on silica gel using asolvent gradient from 0:100 ethyl acetate/cyclohexane to 100:0 ethylacetate/cyclohexane

Preparation of Starting Materials of the Formula (IX) tert-Butyl4-(4-acetyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (IX-1)

At room temperature,1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one (15% solution indichloromethane, 28 g) are added dropwise to a solution of tert-butyl4-[4-(1-hydroxyethyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (VIII-1,2.06 g) in dichloromethane (40 ml). The reaction mixture is stirred atroom temperature overnight, 5 g of silica gel are then added and thesolvent is removed under reduced pressure. The residue is purifiedchromatographically. This gives tert-butyl4-(4-acetyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (1.65 g).

¹H NMR (DMSO-d6): δ 8.34 (s, 1H), 4.00 (d, 2H), 3.26 (m, 1H), 2.93 (td,2H), 2.54 (s, 3H), 2.09-2.03 (m, 2H), 1.60 (qd, 2H), 1.41 (s, 9H)

MS (ESI): 255 (M−C(CH3)3+H)

Preparation of Starting Materials of the Formulae (IVa), (IVb) and (IVc)tert-Butyl4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (IV-1)

At 0° C., a solution of tert-butyl4-carbamothioylpiperidine-1-carboxylate (1.95 g) is added dropwise to asolution of 1-bromo-4-phenylbutan-2-one (2.00 g) in ethanol (20 ml).Under argon, the reaction mixture is stirred at room temperatureovernight. Triethylamine (1.7 ml) is added, and the mixture is dilutedwith ethyl acetate and washed with concentrated sodium chloridesolution. The aqueous phase is removed and extracted with ethyl acetate.The combined organic phases are dried over sodium sulphate andconcentrated under reduced pressure, which gives a mixture of tert-butyl4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate andtert-butyl4-[4-hydroxy-4-(2-phenylethyl)-4,5-dihydro-1,3-thiazol-2-yl]piperidine-1-carboxylate.The two compounds are separated chromatographically. This givestert-butyl4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (800 mg)and tert-butyl4-[4-hydroxy-4-(2-phenylethyl)-4,5-dihydro-1,3-thiazol-2-yl]piperidine-1-carboxylate(640 mg). Both compounds can be used for Process 1.2 since the lattercompound is, under the reaction conditions, converted into the former.

¹H NMR (DMSO-d₆): δ 7.28-7.25 (m, 2H), 7.22-7.22 (m, 2H), 7.20-7.18 (m,1H), 7.13 (s, 1H), 4.00 (bs, 2H), 3.35 (s, 2H), 3.16 (m, 1H), 2.95 (s,4H), 2.00 (d, 2H), 1.52 (qd, 2H), 1.41 (s, 9H) ppm

MS (ESI): 373 ([M+H]⁺)

tert-Butyl4-{4-[(E)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-2)

Under argon, diethyl 1-naphthylmethylphosphonate (1.88 g) is dissolvedin tetrahydrofuran (20 ml) and cooled to 0° C. 757 mg of potassiumtert-butoxide are added, whereupon the colour of the solution changes todark-red. After a further 10 min of stirring, tert-butyl4-(4-formyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (1.00 g) is added.The mixture is stirred at 0° C. for 30 min and then warmed to roomtemperature. After a further 20 min, conc. ammonium chloride solution isadded. The aqueous phase is separated off and extracted with ethylacetate. The combined organic phases are dried over sodium sulphate andconcentrated, and the residue is purified chromatographically. Thisgives tert-butyl4-{4-[(E)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(1.16 g) as the E isomer.

¹H NMR (DMSO-d₆): δ 8.23 (d, 1H), 8.14 (d, 1H), 7.94 (d, 1H), 7.87 (d,1H), 7.83 (d, 1H), 7.62 (s, 1H), 7.62-7.51 (m, 3H), 7.26 (d, 1H), 4.04(d, 2H), 3.27 (m, 1H), 2.94 (t, 2H), 2.15-2.05 (m, 2H), 1.66 (qd, 2H),1.42 (s, 9H) ppm

MS (ESI): 421 ([M+H]⁺)

tert-Butyl4-{4-[(Z)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-3)

Under argon, (1-naphthylmethyl)triphenylphosphonium chloride (2.96 g) isdissolved in 20 ml of tetrahydrofuran and cooled to 0° C., and potassiumtert.-butoxide (757 mg) is added, whereupon the colour of the solutionchanges to dark-red. After 10 min of stirring, tert-butyl4-(4-formyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (1.00 g) is added.The mixture is stirred at 0° C. for another 30 min and then slowlywarmed to room temperature. After a further 20 min, saturated ammoniumchloride solution is added, and the aqueous phase is separated off.After extraction of the aqueous phase with ethyl acetate, the combinedorganic phases are dried over sodium sulphate and concentrated underreduced pressure. After chromatographic purification, this givestert-butyl4-{4-[(Z)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(1.2 g, Z isomer).

¹H NMR (DMSO-d₆): δ 7.92 (t, 2H), 7.87-7.80 (m, 1H), 7.50-7.48 (m, 4H),7.10 (d, 1H), 6.91 (d, 1H), 6.86 (s, 1H), 3.75 (d, 2H), 2.98 (m, 1H),2.80 (t, 2H), 1.80-1.70 (m, 2H), 1.40 (s, 9H), 1.30 (qd, 2H) ppm

MS (ESI): 421 ([M+H]⁺)

tert-Butyl4-{4-[(1Z)-4-phenylpent-1-en-1-yl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-4)

tert-Butyl 4-(4-formyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (1.00g) is reacted with triphenyl(3-phenylbutyl)phosphonium iodide (3.53 g)and purified as described in IV-3. This gives tert-butyl4-{4-[(1Z)-4-phenylpent-1-en-1-yl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(1.23 g) in form of the Z isomer.

¹H NMR (DMSO-d₆): δ 7.30 (s, 1H), 7.26-7.22 (m, 4H), 7.15 (m, 1H), 6.33(s, 1H), 5.59 (m, 1H), 3.98 (d, 2H), 3.19 (m, 1H), 3.00-2.83 (m, 5H),2.06-1.97 (m, 2H), 1.60 (qd, 2H), 1.41 (s, 9H), 1.24 (d, 3H) ppm

MS (ESI): 413 ([M+H]⁺)

tert-Butyl4-[4-(3-phenylprop-1-yn-1-yl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(IV-5)

Under argon, benzyl chloride (134 mg),bis(acetonitrile)dichloropalladium(II) (5.5 mg),2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (30 mg) andcaesium carbonate (363 mg) are added to a degassed solution oftert-butyl 4-(4-ethynyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (X-1,310 mg) in tetrahydrofuran (4 ml). The mixture is then warmed to 65° C.After subsequent cooling, the catalyst is removed by filtration overCelite and the filtrate is concentrated under reduced pressure. Afterchromatographic purification, this gives tert-butyl4-[4-(3-phenylprop-1-yn-1-yl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(329 mg).

¹H NMR (CD₃CN): δ 7.40-7.20 (m, 6H), 4.10-4.05 (m, 2H), 3.83 (s, 2H),3.15 (m, 1H), 2.94-2.35 (m, 2H), 2.08-2.00 (m, 2H), 1.63 (qd, 2H), 1.43(s, 9H) ppm

MS (ESI): 383 ([M+H]⁺)

tert-Butyl4-[4-(naphthalen-1-ylethynyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(IV-6)

Tetrakis(triphenylphosphine)palladium(0) (95 mg), copper(I) iodide (31mg) and triethylamine (200 mg) are added to a solution of tert-butyl4-{4-[(trimethylsilyl)ethynyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(XI-1, 600 mg) and 1-bromonaphthalene (375 mg) in degassedN,N-dimethylformamide. After heating to 85° C., tetra-n-butylammoniumfluoride (1M in THF, 1.81 ml) is added dropwise. The reaction mixture isthen diluted with water and extracted with ethyl acetate. The organicextracts are dried over sodium sulphate and concentrated under reducedpressure. After chromatographic purification, this gives tert-butyl4-[4-(naphthalen-1-ylethynyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(576 mg).

¹H NMR (CD₃CN): δ 8.38 (d, 1H), 7.95 (d, 2H), 7.79 (d, 1H), 7.70 (s,1H), 7.67-7.50 (m, 3H), 4.12 (d, 2H), 3.24 (m, 1H), 2.94 (t, 2H),2.15-2.08 (m, 2H), 1.72 (qd, 2H), 1.45 (s, 9H) ppm

MS (ESI): 419 ([M+H]⁺)

tert-Butyl4-[4-(pyridin-3-ylethynyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(IV-7)

tert-Butyl4-{4-[(trimethylsilyl)ethynyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(XI-1, 610 mg) is reacted analogously to Example IV-6 with3-bromopyridine (291 mg). This gives tert-butyl4-[4-(pyridin-3-ylethynyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(469 mg).

¹H NMR (CD₃CN): δ 8.74 (d, 1H), 8.55 (dd, 1H), 7.87 (s, 1H), 7.63 (m,1H), 7.35 (dd, 1H), 4.10 (d, 2H), 3.20 (m, 2H), 2.93 (t, 2H), 2.13-2.05(m, 2H), 1.69 (qd, 2H), 1.44 (s, 9H) ppm

MS (ESI): 270 ([M+2H—C═OOC(CH₃)₃]⁺)

tert-Butyl4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-8)

tert-Butyl4-{4-[(Z)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-3, 1.5 g) is dissolved in 90 ml of methanol and, at 30° C.,hydrogenated under a hydrogen pressure of 10 bar using 10% Pd/C ascatalyst. Removal of the catalyst by filtration and removal of thesolvent under reduced pressure gives tert-butyl4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(1.48 g) as a colourless oil.

¹H NMR (DMSO-d₆): δ 8.08 (d, 1H), 7.88 (d, 1H), 7.74 (d, 1H), 7.55-7.45(m, 2H), 7.42-7.32 (m, 2H), 7.10 (s, 1H), 4.00 (d, 2H), 3.43 (t, 2H),3.32-3.06 (m, 3H), 2.92 (t, 2H), 2.04-1.98 (m, 2H), 1.58 (qd, 2H), 1.42(s, 9H) ppm

MS (ESI): 423 ([M+H]⁺)

Preparation of Starting Materials of the Formula (X) tert-Butyl4-(4-ethynyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (X-1)

Under argon, tert-butyl4-(4-formyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (600 mg) isdissolved in methanol, and potassium carbonate (839 mg) and dimethyl1-diazo-2-oxopropylphosphonate (786 mg) are added. The mixture isstirred at room temperature for 3 hours. After aqueous work-up, themixture is extracted with ethyl acetate and the extracts are dried withsodium sulphate and concentrated under reduced pressure. The residue ispurified chromatographically. This gives tert-butyl4-(4-ethynyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (493 mg).

¹H NMR (CD₃CN): δ 7.51 (s, 1H), 4.07 (d, 2H), 3.36 (s, 1H), 3.16 (m,1H), 2.90 (t, 2H), 2.10-2.00 (m, 2H), 1.65 (qd, 2H), 1.43 (s, 9H) ppm

MS (ESI): 237 ([M+2H—C(CH₃)₃]⁺)

Preparation of Starting Materials of the Formula (XI) tert-Butyl4-{4-[(trimethylsilyl)ethynyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(XI-1)

Under argon, tert-butyl4-(4-ethynyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (X-1, 940 mg) isdissolved in tetrahydrofuran at −78° C., and lithiumhexamethyldisilazane(1M in hexane, 4.82 ml) is added dropwise. After 30 min, trimethylsilylchloride (699 mg) is added dropwise, and cooling is removed. The mixtureis stirred overnight, saturated ammonium chloride solution is then addedand the mixture is extracted with ethyl acetate. The organic extractsare dried over sodium sulphate and concentrated under reduced pressure.The residue is purified chromatographically. This gives tert-butyl4-{4-[(trimethylsilyl)ethynyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(1.28 g).

¹H NMR (CD₃CN): δ 7.42 (s, 1H), 4.05-3.97 (m, 2H), 3.09 (m, 1H), 2.83(t, 2H), 2.05-1.90 (m, 2H), 1.59 (qd, 2H), 1.37 (s, 9H), 0.17 (s, 9H)ppm

MS (ESI): 309 ([M+2H—C(CH₃)₃]⁺)

Preparation of Starting Materials of the Formula (IIa), (IIb) and (IIc)4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1)

At 0° C., a 2-molar solution of hydrogen chloride in diethyl ether isadded dropwise to a solution of tert-butyl4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-carboxylate (IV-1, 640mg). The reaction mixture is stirred at 0° C. and then slowly warmed toroom temperature. The mixture is stirred overnight, and the solvent andexcess hydrogen chloride are then removed. This gives4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (590 mg).

¹H NMR (DMSO-d₆): δ 7.25-7.23 (m, 2H), 7.19-7.16 (m, 3H), 7.11 (s, 1H),3.40-3.30 (m, 5H), 2.98 (s, 4H), 2.21-2.14 (m, 2H), 1.95-1.87 (m, 2H)ppm

MS (ESI): 273 ([M−Cl]⁺)

4-{4-[2-(Naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidinehydrochloride (II-2)

Under argon and at 0° C., a solution of hydrogen chloride in diethylether (2 M, 25 ml) is added to tert-butyl4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-2, 1.40 g). The mixture is stirred at 0° C. and then slowly warmedto room temperature. The mixture is stirred overnight, and the excessacid and solvent are then removed under reduced pressure. This gives4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidinehydrochloride (1.28 g).

¹H NMR (DMSO-d₆): δ 9.18 (bs, 1H), 8.93 (bs, 1H), 8.08 (d, 1H), 7.89 (d,1H), 7.75 (d, 1H), 7.56-7.45 (m, 2H), 7.73-7.32 (m, 2H), 7.16 (s, 1H),3.45 (d, 1H), 3.43 (d, 1H), 3.38-3.28 (m, 2H), 3.15-2.95 (m, 4H),2.25-2.17 (m, 2H), 2.00 (qd, 2H) ppm

MS (ESI): 323 ([M−Cl]⁺)

4-[5-Bromo-4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine (II-3)

At 0° C., bromine (123 mg) is added dropwise to a solution of4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,200 mg) in acetic acid (2 ml). The mixture is stirred for 30 min, andsaturated sodium bicarbonate solution is then added. The aqueous phaseis separated off and extracted with ethyl acetate. The combined organicphases are dried over anhydrous sodium carbonate, concentrated underreduced pressure and purified chromatographically. This gives4-[5-bromo-4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine (127 mg).

log P (pH2.3): 1.72

MS (ESI): 351, 353 ([M+1]⁺)

Preparation of Compounds of the Formula (Ia) Method A2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-53)

At 0° C., oxalyl chloride (134 mg) and a drop of N,N-dimethylformamideare added to a solution of[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (185 mg) indichloromethane. The reaction mixture is stirred at room temperature for3 h. Solvent and excess reagent are removed under reduced pressure. Thesolid residue is then once more dissolved in dichloromethane and, at 0°C., added dropwise to a solution of4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,250 mg) and triethylamine (410 mg) in dichloromethane. Concentratedammonium chloride solution is then added to the reaction solution, andthe aqueous phase is removed and extracted with ethyl acetate. Thecombined organic phases are dried over anhydrous sodium sulphate andconcentrated. This gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(122 mg).

¹H NMR (DMSO-d₆): δ 7.28-7.26 (m, 2H), 7.22-7.21 (m, 2H), 7.19-7.15 (m,2H), 6.51 (s, 1H), 5.33 (d, 1H), 5.25 (d, 1H), 4.36 (d, 1H), 3.95 (d,1H), 3.35-3.20 (m, 2H), 2.96 (s, 4H), 2.82 (t, 1H), 2.21 (s, 3H), 2.09(d, 1H), 2.07 (d, 1H), 1.78 (m, 1H), 1.53 (m, 1H) ppm

MS (ESI): 463 ([M+H]⁺)

1-{4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}pentan-1-one(I-58)

Pentanoyl chloride (133 mg) is added to a solution of4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,309 mg) and triethylamine (0.7 ml) in dichloromethane (3 ml). Themixture is stirred overnight, and water is then added. The aqueous phaseis separated off and extracted with ethyl acetate, and the combinedorganic phases are then dried with sodium sulphate and concentrated. Theresidue is purified. This gives1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}pentan-1-one(179 mg).

¹H NMR (DMSO-d₆): δ 7.27-7.21 (m, 2H), 7.20-7.14 (m, 3H), 7.05 (s, 1H),4.37 (bs, 1H), 3.95 (bs, 1H), 3.26-3.18 (m, 2H), 2.96 (s, 4H), 2.80 (bs,1H), 2.33 (t, 2H), 2.04 (d, 2H), 1.55 (bs, 2H), 1.50 (tt, 2H), 1.33 (tq,2H), 0.90 (t, 3H) ppm

MS (ESI): 357 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(I-81)

Oxalyl chloride (183 mg) and a drop of N,N-dimethylformamide are addedto a solution of [5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]aceticacid (100 mg) in dichloromethane (5 ml). The reaction mixture is stirredat room temperature overnight. After removal of the solvents underreduced pressure, the residue is then dissolved in dichloromethane (5ml) and a solution of4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidinehydrochloride (II-2, 172 mg) and Hünig base (186 mg) in dichloromethane(5 ml) is added dropwise at 0° C. Following the addition of conc.ammonium chloride solution, the aqueous phase is separated off andextracted with ethyl acetate. The combined organic phases are dried oversodium sulphate and concentrated under reduced pressure. The residue ispurified chromatographically. This gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(150 mg).

¹H NMR (DMSO-d₆): δ 8.09 (d, 1H), 7.90 (d, 1H), 7.75 (d, 1H), 7.56-7.46(m, 2H), 7.42-7.33 (m, 2H), 7.12 (s, 1H), 6.45 (s, 1H), 5.22 (bs, 2H),4.31 (bs, 1H), 3.98 (bs, 1H), 3.44 (t, 2H), 3.35-3.26 (m, 2H), 3.15-3.05(m, 2H), 2.90 (bs, 1H), 2.23 (s, 3H), 2.15-2.05 (m, 2H), 1.75 (bs, 1H),1.62 (bs, 1H) ppm

MS (ESI): 513 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(4-phenylpentyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-80)

tert-Butyl4-{4-[(1Z)-4-phenylpent-1-en-1-yl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-4, 1.00 g) is dissolved in methanol and, at 40° C., hydrogenatedunder an H₂-pressure of 10 bar in the presence of Pd/C (10%) for 5hours. Filtration and removal of the solvent under reduced pressuregives tert-butyl4-[4-(4-phenylpentyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (1.00 g)as a colourless oil. This is deprotected analogously to Example II-2.This gives 850 mg of 4-[4-(4-phenylpentyl)-1,3-thiazol-2-yl]piperidinehydrochloride. 169 mg are then reacted analogously to Example I-81 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (100 mg).After chromatographic purification, this gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(4-phenylpentyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(180 mg) as a colourless oil.

¹H NMR (DMSO-d₆): δ 7.28-7.23 (m, 2H), 7.19-7.14 (m, 3H), 7.02 (s, 1H),6.44 (s, 1H), 5.20 (bs, 2H), 4.30 (bs, 1H), 3.95 (bs, 1H), 3.30-3.20 (m,2H), 2.87 (bs, 1H), 2.72 (m, 1H), 2.67-2.62 (m, 2H), 2.22 (s, 3H),2.07-2.02 (m, 2H), 1.72 (bs, 1H), 1.63-1.47 (m, 5H), 1.19 (d, 3H) ppm

MS (ESI): 505 ([M+H]⁺)

1-{4-[5-Bromo-4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(I-78)

4-[5-Bromo-4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidine (II-3, 127 mg)is reacted analogously to Example I-81 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (118 mg).After chromatographic purification, this gives1-{4-[5-bromo-4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(52 mg).

¹H NMR (DMSO-d₆): δ 7.27-7.22 (m, 2H), 7.18-7.13 (m, 3H), 6.45 (s, 1H),5.22 (bs, 2H), 4.38 (bs, 1H), 3.95 (bs, 1H), 3.33-3.20 (m, 2H), 2.94 (s,4H), 2.93 (bs, 1H), 2.22 (s, 3H), 2.09-2.02 (m, 2H), 1.80-1.50 (m, 2H)ppm

MS (ESI): 541 ([M+H]⁺)

Method B1-{4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}-2-(thiophen-3-yl)ethanone(I-63)

Thiophen-3-ylacetic acid (156 mg) and Hünig base (323 mg) are dissolvedin dichloromethane (10 ml) and stirred for 30 min.4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,309 mg), prepared according to Process 1.2, is added, and the mixture isstirred for a further 5 min before bromo-tris-pyrrolidino-phosphoniumhexafluorophosphate (599 mg) is added. The reaction mixture is stirredat room temperature overnight. After removal of the solvent underreduced pressure, the residue is purified chromatographically. Thisgives1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}-2-(thiophen-3-yl)ethanone(99 mg).

¹H NMR (DMSO-d₆): δ 7.44-7.43 (m, 1H), 7.28-7.12 (m, 6H), 7.05 (s, 1H),6.99 (d, 1H), 4.38 (bs, 1H), 3.99 (bs, 1H), 3.72 (s, 2H), 3.22-3.15 (m,2H), 2.96 (s, 4H), 2.81 (bs, 1H), 2.00 (d, 2H), 1.52 (m, 2H) ppm

MS (ESI): 397 ([M+H]⁺)

2-[2-Chloro-5-(trifluoromethyl)phenyl]-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-67)

4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,309 mg) is reacted analogously to Example I-63 with[2-chloro-5-(trifluoromethyl)phenyl]acetic acid (262 mg). Afterchromatographic purification, this gives2-[2-chloro-5-(trifluoromethyl)phenyl]-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(210 mg).

¹H NMR (DMSO-d₆): δ 7.71-7.58 (m, 3H), 7.27-7.12 (m, 5H), 7.07 (s, 1H),4.37 (bs, 1H), 4.05 (bs, 1H), 3.97 (s, 2H), 3.35-3.23 (m, 2H), 2.97 (s,4H), 2.88 (bs, 1H), 2.07 (d, 2H), 1.65 (bs, 2H) ppm

MS (ESI): 439 ([M+H]⁺)

2-(5-Chloro-1-methyl-1H-pyrazol-4-yl)-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-65)

4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,280 mg) is reacted analogously to Example I-63 with(5-chloro-1-methyl-1H-pyrazol-4-yl)acetic acid (174 mg). Afterchromatographic purification, this gives2-(5-chloro-1-methyl-1H-pyrazol-4-yl)-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(89 mg).

¹H NMR (DMSO-d₆): δ 7.40 (s, 1H), 7.26-7.15 (m, 5H), 7.06 (s, 1H), 4.35(bs, 1H), 4.05 (bs, 1H), 3.76 (s, 3H), 3.49 (s, 2H), 3.30-3.19 (m, 2H),2.99 (s, 4H), 2.82 (bs, 1H), 2.08-2.00 (m, 2H), 1.58 (bs, 2H) ppm

MS (ESI): 429 ([M+H]⁺)

2-[4-Chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}propan-1-one(I-64)

4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,309 mg) is reacted analogously to Example I-63 with2-[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]propanoic acid(282 mg). After chromatographic purification, this gives2-[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}propan-1-one(165 mg).

¹H NMR (DMSO-d₆): δ 7.26-7.21 (m, 2H), 7.20-7.13 (m, 3H), 7.06 (s, 1H),5.70 (m, 1H), 4.30 (bs, 1H), 4.00 (bs, 1H), 3.30-3.19 (m, 2H), 2.96 (s,5H), 2.26 (d, 3H), 2.08-1.96 (m, 2H), 1.64-1.54 (m, 5H) ppm

MS (ESI): 511 ([M+H]⁺)

[2,5-Bis(trifluoromethyl)phenyl]{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}methanone(I-61)

4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,309 mg) is reacted analogously to Example I-63 with2,5-bis(trifluoromethyl)benzenecarbonyl chloride (304 mg). Afterchromatographic purification, this gives[2,5-bis(trifluoromethyl)phenyl]{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}methanone(282 mg).

¹H NMR (DMSO-d₆): δ 8.07-7.90 (m, 3H), 7.26-7.21 (m, 2H), 7.20-7.14 (m,3H), 7.08 (s, 1H), 4.50 (d, 1H), 3.35-3.23 (m, 4H), 2.97 (s, 4H),2.22-2.10 (m, 1H), 2.00-1.87 (m, 2H), 1.87-1.45 (m, 2H) ppm

MS (ESI): 513 ([M+H]⁺)

3-(3,4-Dimethoxyphenyl)-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}propan-1-one(I-66)

4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,309 mg) is reacted analogously to Example I-63 with3-(3,4-dimethoxyphenyl)propanoic acid (231 mg). After chromatographicpurification, this gives3-(3,4-dimethoxyphenyl)-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}propan-1-one(139 mg).

¹H NMR (DMSO-d₆): δ 7.26-7.21 (m, 2H), 7.20-7.12 (m, 3H), 7.05 (s, 1H),6.85-6.80 (m, 3H), 6.75-6.71 (dd, 1H), 3.93 (bs, 1H), 3.74 (s, 3H), 3.69(s, 3H), 3.20 (m, 1H), 2.96 (s, 4H), 2.80-2.74 (m, 2H), 2.65-2.55 (bs,2H), 2.04-1.97 (m, 2H), 1.58-1.42 (m, 2H), 1.28 (t, 2H) ppm

MS (ESI): 465 ([M+H]⁺)

2-(1,3-Benzothiazol-2-yl)-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-71)

4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,308 mg) is reacted analogously to Example I-63 with1,3-benzothiazol-2-ylacetic acid (252 mg). After chromatographicpurification, this gives2-(1,3-benzothiazol-2-yl)-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(109 mg).

¹H NMR (DMSO-d₆): δ 8.03 (d, 1H), 7.93 (d, 1H), 7.47 (t, 1H), 7.40 (t,1H), 7.25-7.16 (m, 5H), 7.06 (s, 1H), 4.40 (bs, 1H), 4.34 (s, 2H), 4.09(bs, 1H), 3.40-3.15 (m, 3H), 2.96 (s, 4H), 2.08-2.02 (m, 2H), 1.65 (bs,2H) ppm

MS (ESI): 448 ([M+H]⁺)

2-(2H-Indazol-2-yl)-1-{4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-70)

4-[4-(2-Phenylethyl)-1,3-thiazol-2-yl]piperidine hydrochloride (II-1,309 mg), prepared according to Process 1.2, is reacted analogously toExample I-63 with 2H-indazol-2-ylacetic acid (194 mg). Afterchromatographic purification, this gives2-(2H-indazol-2-yl)-1-{-4-[4-(2-phenylethyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(67 mg).

¹H NMR (CD₃CN): δ 8.10 (s, 1H), 7.71 (d, 1H), 7.60 (d, 1H), 7.29-7.15(m, 6H), 7.07 (dd, 1H), 6.87 (s, 1H), 5.45 (d, 1H), 5.36 (d, 1H), 4.48(d, 1H), 4.00 (d, 1H), 3.35-3.23 (m, 2H), 3.00 (s, 4H), 2.86 (t, 1H),2.18-2.06 (m, 2H), 1.80 (qd, 1H), 1.66 (qd, 1H) ppm

MS (ESI): 431 ([M+H]⁺)

Method C2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(I-81)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(naphthalen-1-ylethynyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-50, 157 mg) is dissolved in methanol (1.5 ml) and, at 60° C., reactedwith ammonium formiate (195 mg) and 20% Pd(OH)₂/C (4 mg) as catalyst.The catalyst is filtered off and the solvent is removed under reducedpressure, giving2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[2-(naphthalen-1-yl)ethyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(86 mg) as a colourless oil.

The product was characterized like the compound described beforehand.

Preparation of Compounds of the Formula (Ib)2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(E)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(I-27)

tert-Butyl4-{4-[(E)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-2, 171 mg) is deprotected analogously to Example II-2 and thenreacted analogously to Example I-81 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (100 mg).After chromatographic purification, this gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(E)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(180 mg).

¹H NMR (DMSO-d₆): δ 8.23 (d, 1H), 8.16 (d, 1H), 7.95 (d, 1H), 7.88 (d,1H), 7.83 (d, 1H), 7.64 (s, 1H), 7.63-7.51 (m, 3H), 7.27 (d, 1H), 6.46(s, 1H), 5.24 (bs, 2H), 4.38 (bs, 1H), 4.03 (bs, 1H), 3.40 (m, 1H), 3.32(bs, 1H), 2.94 (bs, 1H), 2.24 (s, 3H), 2.23-2.12 (m, 2H), 1.85 (bs, 1H),1.70 (bs, 1H) ppm

MS (ESI): 511 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(Z)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(I-2)

tert-Butyl4-{4-[(Z)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-3, 171 mg) is deprotected analogously to Example II-2 and thenreacted analogously to Example I-81 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (100 mg).After chromatographic purification, this gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(E)-2-(naphthalen-1-yl)ethenyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(200 mg).

¹H NMR (DMSO-d₆): δ 7.95-7.92 (m, 2H), 7.87-7.84 (m, 1H), 7.52-7.43 (m,4H), 7.11 (d, 1H), 6.93 (d, 1H), 6.88 (s, 1H), 6.45 (s, 1H), 5.14 (s,2H), 4.05 (bs, 1H), 3.74 (bs, 1H), 3.20-3.05 (m, 2H), 2.88 (bs, 1H),2.24 (s, 3H), 1.90-1.78 (bs, 2H), 1.50 (bs, 1H), 1.35 (bs, 1H) ppm

MS (ESI): 511 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(1Z)-4-phenylpent-1-en-1-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(I-3)

tert-Butyl4-{4-[(1Z)-4-phenylpent-1-en-1-yl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IV-4, 168 mg) is deprotected analogously to Example II-2 and thenreacted analogously to Example I-81 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (100 mg). Thisgives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(1Z)-4-phenylpent-1-en-1-yl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(200 mg).

¹H NMR (DMSO-d₆): δ 7.32 (s, 1H), 7.29-7.22 (m, 4H), 7.15 (m, 1H), 6.44(s, 1H), 6.35 (d, 1H), 5.60 (m, 1H), 5.20 (bs, 2H), 4.30 (bs, 1H), 3.98(bs, 1H), 3.38-3.25 (m, 2H), 3.05-2.84 (m, 4H), 2.22 (s, 3H), 2.17-2.05(m, 2H), 1.85-1.56 (m, 2H), 1.26 (d, 3H) ppm

MS (ESI): 503 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(Z)-2-(2-naphthyl)vinyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(I-20)

(2-Naphthylmethyl)(triphenyl)phosphonium chloride (454 mg) is dissolvedin 5 ml of tetrahydrofuran and cooled to 0° C. under argon, andpotassium tert.-butoxide (125 mg) is added, whereupon the colour of thesolution turns to dark red. After 10 min of stirring,2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carbaldehyde(200 mg) is added. The mixture is stirred at 0° C. for another 30 minand then slowly warmed to room temperature. After a further 20 min,saturated ammonium chloride solution is added, and the aqueous phase isseparated off. After extraction of the aqueous phase with ethyl acetate,the combined organic phases are dried over sodium sulphate andconcentrated under reduced pressure. After chromatographic purification,this gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(Z)-2-(2-naphthyl)vinyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(260 mg).

MS (ESI): 511 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(E)-2-phenylethenyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanethione(I-93)

Methoxyphenyldithiophosphonic anhydride (62 mg) is added to a solutionof2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(E)-2-phenylethenyl]-1,3-thiazol-2-yl}piperidin-1-yl)-ethanone(141 mg) in chloroform (1 ml) and 1,2-dimethoxyethane (2 ml). Thereaction mixture is stirred at room temperature for 24 hours and at 40°C. for 3 hours. After removal of the solvent under reduced pressure, theresidue is purified chromatographically. This gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(E)-2-phenylethenyl]-1,3-thiazol-2-yl}piperidin-1-yl)-ethanethione(45 mg) as a colourless oil.

¹H NMR (CD₃CN): δ 7.55 (d, 2H), 7.43 (d, 1H), 7.37 (t, 2H), 7.30-7.28(m, 2H), 7.18 (d, 1H), 6.39 (s, 1H), 5.41 (d, 1H), 5.26 (s, 2H), 4.42(d, 1H), 3.54 (t, 1H), 3.45 (m, 1H), 3.38 (t, 1H), 2.31 (s, 3H),2.30-2.23 (m, 2H), 1.95-1.80 (m, 2H) ppm

MS (ESI): 477 ([M+H]⁺)

Preparation of Compounds of the Formula (Ic)2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(naphthalen-1-ylethynyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-50)

tert-Butyl4-[4-(naphthalen-1-ylethynyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(IV-6, 200 mg) is deprotected analogously to Example II-2 and thenreacted analogously to Example I-81 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (117 mg).After chromatographic purification, this gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(naphthalen-1-ylethynyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(112 mg).

¹H NMR (CD₃CN): δ 8.39 (d, 1H), 7.96 (d, 2H), 7.80 (d, 1H), 7.72 (s,1H), 7.67-7.50 (m, 3H), 6.37 (s, 1H), 5.05 (s, 2H), 4.45 (bs, 1H), 3.98(bs, 1H), 3.40-3.20 (m, 2H), 2.93 (bs, 1H), 2.25 (s, 3H), 2.25-2.15 (m,2H), 1.90-1.75 (m, 2H) ppm

MS (ESI): 509 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(pyridin-3-ylethynyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-51)

tert-Butyl4-[4-(pyridin-3-ylethynyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(IV-7, 469 mg) is deprotected analogously to Example II-2 giving3-{[2-(piperidin-4-yl)-1,3-thiazol-4-yl]ethynyl}-pyridine hydrochloride(407 mg). This is immediately reacted at room temperature with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (277 mg) inthe presence of 4-dimethylaminopyridine (16 mg) and1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide (268 mg) indichloromethane (5 ml). Stirring at room temperature overnight,concentration and chromatographic purification gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(pyridin-3-ylethynyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(65 mg).

¹H NMR (CD₃CN): δ 8.74 (dd, 1H), 8.59 (dd, 1H), 7.99 (s, 1H), 7.96 (m,1H), 7.45 (dd, 1H), 6.45 (s, 1H), 5.22 (bs, 2H), 4.35 (bs, 1H), 4.00(bs, 1H), 3.40-3.20 (m, 3H), 2.22 (s, 3H), 2.17-2.10 (m, 2H), 1.90-1.55(m, 2H) ppm

MS (ESI): 460 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(3-phenylprop-1-yn-1-yl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-52)

tert-Butyl4-[4-(3-phenylprop-1-yn-1-yl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(IV-5, 320 mg) is then deprotected dann analogously to Example II-2 andthen reacted analogously to Example I-81 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (174 mg).After chromatographic purification, this gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(3-phenylprop-1-yn-1-yl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(33 mg).

¹H NMR (CD₃CN): δ 7.46 (s, 1H), 7.42-7.34 (m, 4H), 7.30-7.25 (m, 1H),6.39 (s, 1H), 5.09 (d, 1H), 5.02 (d, 1H), 4.45 (d, 1H), 3.91 (d, 1H),3.84 (s, 2H), 3.25 (m, 2H), 2.82 (t, 1H), 2.23 (s, 3H), 2.18-2.05 (m,2H), 1.82 (qd, 1H), 1.66 (qd, 1H) ppm

MS (ESI): 473 ([M+H]⁺)

1-[4-(4-Ethynyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(I-86)

Under argon,2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-carbaldehyde(200 mg) is dissolved in methanol (5 ml) and potassium carbonate (215mg) and dimethyl 1-diazo-2-oxopropylphosphonate (199 mg) are added. Themixture is stirred at 40° C. After aqueous work-up, the mixture isextracted with ethyl acetate and the extracts are dried with sodiumsulphate and concentrated under reduced pressure. The residue ispurified chromatographically. This gives1-[4-(4-ethynyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(67 mg).

¹H NMR (DMSO-d6): δ 7.86 (s, 1H), 6.44 (s, 1H), 5.20 (bs, 2H), 4.31 (bs,1H), 4.08 (s, 1H), 3.98 (bs, 1H), 3.31 (m, 1H), 3.28 (bs, 1H), 2.88 (bs,1H), 2.22 (s, 3H), 2.13-2.05 (m, 2H), 1.78 (bs, 1H), 1.61 (bs, 1H) ppm

MS (ESI): 383 ([M+H]⁺)

2-[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(trimethylsilyl)ethynyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(I-98)

Under argon,1-[4-(4-ethynyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(I-86, 525 mg) is, at −78° C., dissolved in tetrahydrofuran (10 ml), andlithium hexamethyldisilazane (1M in hexane, 1.40 ml) is added dropwise.After 10 min, trimethylsilyl chloride (179 mg) is added dropwise. After30 minutes of stirring, saturated ammonium chloride solution is addedand the mixture is extracted with ethyl acetate. The organic extractsare dried over sodium sulphate and concentrated under reduced pressure.The residue is purified chromatographically. This gives2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(trimethylsilyl)ethynyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(540 mg).

¹H NMR (DMSO-d6): δ 7.70 (s, 1H), 6.27 (s, 1H), 5.08 (d, 1H), 5.01 (d,1H), 4.12 (bd, 1H), 3.76 (bd, 1H), 3.05 (t, 1H), 2.59 (t, 1H), 1.97 (s,3H), 1.88-1.77 (m, 2H), 1.56 (tdd, 1H), 1.30 (tdd, 1H), 0.00 (s, 9H) ppm

MS (ESI): 455 ([M+1]⁺)

1-(4-{4-[(4-Methoxyphenyl)ethynyl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(I-100)

Tetrakis(triphenylphosphine)palladium(0) (25 mg), copper(I) iodide (8mg) and triethylamine (53 mg) are added to a solution of2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(trimethylsilyl)ethynyl]-1,3-thiazol-2-yl}piperidin-1-yl)ethanone(I-98, 200 mg) and 1-bromo-4-methoxybenzene (91 mg) in degassedN,N-dimethylformamide (2 ml). After warming to 85° C.,tetra-n-butylammonium fluoride (1M in THF, 0.48 ml) is added dropwise.The reaction mixture is then diluted with water and extracted with ethylacetate. The organic extracts are dried over sodium sulphate andconcentrated under reduced pressure. After chromatographic purification,this gives1-(4-{4-[(4-methoxyphenyl)ethynyl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(84 mg).

¹H NMR (DMSO-d6): δ 7.84 (s, 1H), 7.49 (d, 2H), 6.98 (d, 2H), 6.45 (s,1H), 5.22 (bs, 2H), 4.33 (bs, 1H), 3.98 (bs, 1H), 3.80 (s, 3H), 3.34 (m,1H), 3.28 (bs, 1H), 2.89 (bs, 1H), 2.22 (s, 3H), 2.15-2.09 (m, 2H), 1.80(bs, 1H), 1.63 (bs, 1H) ppm

MS (ESI): 489 ([M+H]⁺)

1-(4-{4-[(2-Methoxyphenyl)ethynyl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(I-103)

Tetrakis(triphenylphosphine)palladium(0) (25 mg), copper(I) iodide (7mg) and triethylamine (48 mg) are added to a solution of1-[4-(4-ethynyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(I-86, 150 mg) and 1-iodo-2-methoxybenzene (101 mg) in degassedN,N-dimethylformamide (1.5 ml). After 2 hours of stirring at 85° C., thereaction mixture is then diluted with water and extracted with ethylacetate. The organic extracts are dried over sodium sulphate andconcentrated under reduced pressure. After chromatographic purification,this gives1-(4-{4-[(2-methoxyphenyl)ethynyl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(100 mg).

¹H NMR (DMSO-d6): δ 7.86 (s, 1H), 7.47 (dd, 1H), 7.40 (td, 1H), 7.09 (d,1H), 6.98 (td, 1H), 6.45 (s, 1H), 5.23 (bs, 2H), 4.33 (bs, 1H), 3.98(bs, 1H), 3.86 (s, 3H), 3.35 (m, 1H), 3.29 (bs, 1H), 2.89 (bs, 1H), 2.23(s, 3H), 2.15-2.08 (m, 2H), 1.80 (bs, 1H), 1.63 (bs, 1H) ppm

MS (ESI): 489 ([M+H]⁺)

EXAMPLES

The compounds of the formula I listed in Table 1 below can be obtainedanalogously to the methods given above.

TABLE I

where Ex A L¹ Y W X R² L² L³ R³ log p I-1 5-methyl-3- CH₂ O CH₂CH₂CH₂CH₂ H CH═CH (Z) bond phenyl 3.91^([b]) (trifluoromethyl)-1H-pyrazol-1-yl I-2 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bondnaphthalen-1-yl 4.52^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-35-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) CH₂CHCH₃ phenyl 4.84^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-4 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ HCH═CH (Z) bond cyclohexyl (trifluoromethyl)-1H- pyrazol-1-yl I-53-(trifluoromethyl)- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond cyclohexyl1H-pyrazol-1-yl I-6 4-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z)bond cyclohexyl (trifluoromethyl)-1H- pyrazol-1-yl I-73-(trifluoromethyl)- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond phenyl3.72^([b]) 1H-pyrazol-1-yl I-8 4-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H CH═CH (Z) bond phenyl 4.56^([b]) (trifluoromethyl)-1H- pyrazol-1-ylI-9 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond 4-chlorophenyl4.41^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-10 3-(trifluoromethyl)-CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond 4-chlorophenyl 4.2^([b ])1H-pyrazol-1-yl I-11 4-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH(Z) bond 4-chlorophenyl 4.92^([b]) (trifluoromethyl)-1H- pyrazol-1-ylI-12 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond 4-methoxyphenyl3.9^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-13 3-(trifluoromethyl)-CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond 4-methoxyphenyl 1H-pyrazol-1-ylI-14 4-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond4-methoxyphenyl 4.46^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-155-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond 3-(trifluoromethyl)-4.51^([b]) (trifluoromethyl)-1H- phenyl pyrazol-1-yl I-163-(trifluoromethyl)- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond3-(trifluoromethyl)- 4.3^([b]) 1H-pyrazol-1-yl phenyl I-174-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond3-(trifluoromethyl)- 5.03^([b]) (trifluoromethyl)-1H- phenylpyrazol-1-yl I-18 3-(trifluoromethyl)- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z)bond naphthalen-1-yl 4.35^([b]) 1H-pyrazol-1-yl I-194-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bondnaphthalen-1-yl 5.14^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-205-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond naphthalen-2-yl4.61^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-21 3-(trifluoromethyl)-CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bond naphthalen-2-yl 4.35^([b])1H-pyrazol-1-yl I-22 4-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH(Z) bond naphthalen-2-yl 5.08^([b]) (trifluoromethyl)-1H- pyrazol-1-ylI-23 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) CH₂ phenyl 4.41^([b])(trif1uoromethyl)-1H- pyrazol-1-yl I-24 3-(trifluoromethyl)- CH₂ OCH₂CH₂ CH₂CH₂ H CH═CH (Z) CH₂ phenyl 1H-pyrazol-1-yl I-254-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) CH₂ phenyl(trifluoromethyl)-1H- pyrazol-1-yl I-26 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H CH═CH (E) bond phenyl 3.99^([b]) (trifluoromethyl)-1H- pyrazol-1-y1I-27 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (E) bond naphthalen-1-yl4.63^([b]) (trifluoromCthyl)-1H- pyrazol-1-yl I-28 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H CH═CH (E) CH₂ CF₃ (trifluoromethyl)-1H- pyrazol-1-ylI-29 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (E) CH₂ tert-butyl(trifluoromethyl)-1H- pyrazol-1-yl I-30 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H CH═CH (E) CH₂ ethenyl (trifluoromethyl)-1H- pyrazol-1-yl I-315-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (E) CH₂ ethynyl(trifluoromethyl)-1H- pyrazol-1-yl I-32 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H CH═CH (E) CH₂ cyclohexyl (trifluoromethyl)-1H- pyrazol-1-yl I-335-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (E) CH₂ morpholin-4-yl(trifluoromethyl)-1H- pyrazol-1-yl I-34 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H CH═CH (E) bond pyridin-3-yl (trifluoromethyl)-1H- pyrazol-1-yl I-355-(difluoromethyl)-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl3.37^([b]) methyl-1H-pyrazol-1- yl I-36 3,5-dichloro-1H- CH₂ O CH₂CH₂CH₂CH₂ H CH₂CH₂ bond phenyl pyrazol-1-yl I-37 3,5-dibromo-1H- CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl pyrazol-1-yl I-38 2-bromo-5- CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl (trifluoromethyl) phenyl I-395-bromo-2- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl methylphenyl I-402,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl I-412,5-dibromophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl I-425-iodo-2-methylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl I-43 3,5-CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl 4.89^([b])bis(trifluoromethyl)- 1H-pyrazol-1-yl I-44 5-(difluoromethyl)-3- CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl methyl-1H-pyrazol-1- yl I-453,5-dichloro-1H- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond naphthalen-1-ylpyrazol-1-yl I-46 3,5-dibromo-1H- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondnaphthalen-1-yl pyrazol-1-yl I-47 2-chloro-5- CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond naphthalen-1-yl (trifluoromethyl) phenyl I-48 2-bromo-5- CH₂O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl (trifluoromethyl) phenylI-49 5-bromo-2- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond naphthalen-1-ylmethylphenyl I-50 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bondnaphthalen-1-yl 4.66^([c]); (trifluoromethyl)-1H- 4.5^([b]) pyrazol-1-ylI-51 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond pyridin-3-yl 2.68^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-52 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H C≡C CH₂ phenyl 3.88^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-535-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl 3.79^([a])(trifluoromethyl)-1H- pyrazol-1-yl I-54 3,5-dimethyl-1H- CH₂ O CH₂CH₂CH₂CH₂ H CH₂CH₂ bond phenyl 2.86^([a]) pyrazol-1-yl I-553-(trifluoromethyl)- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl 3.57^([b])1H-pyrazol-1-yl I-56 3-(trifluoromethyl) CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂bond phenyl 4.26^([b]) phenyl I-57 3-chlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond phenyl 4.1^([b]) I-58 CH₃ CH₂CH₂CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂bond phenyl 3.73^([b]) I-59 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondphenyl 4.45^([b]) bis(trifluoromethyl)- 1H-pyrazol-1-yl I-604-chloro-5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl 4.34^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-61 2,5- bond O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond phenyl 4.67^([b]) bis(trifluoromethyl) phenyl I-623-(trifluoromethyl) bond O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl 4.23^([b])phenyl I-63 thiophen-3-yl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl3.47^([b]) I-64 4-chloro-5-methyl-3- CHCH₃ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondphenyl 4.62^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-655-chloro-1-methyl-1H- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl2.98^([b]) pyrazol-4-yl I-66 3,4-dimethoxyphenyl CH₂CH₂ O CH₂CH₂ CH₂CH₂H CH₂CH₂ bond phenyl 3.43^([b]) I-67 2-chloro-5- CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond phenyl 4.73^([b]) (trifluoromethyl) phenyl I-683-(trifluoromethyl)- CHCH₃ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl3.93^([b]) 1H-pyrazol-1-yl I-69 1H-pyrazol-1-yl CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond phenyl 2.56^([b]) I-70 2H-indazol-2-yl CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond phenyl 3.14^([b]) I-71 1,3-benzothiazol-2-yl CH₂ O CH₂CH₂CH₂CH₂ H CH₂CH₂ bond phenyl 3.68^([b]) I-72 1H-benzimidazol-2-yl CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond phenyl I-73 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂2- CH₂ bond H 3.75^([b]) (trifluoromethyl)-1H- methylpropyl pyrazol-1-ylI-74 3,5-dimethyl-1H- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond naphthalen-1-yl3.85^([c]) pyrazol-1-yl I-75 pyridin-4-yl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂bond phenyl I-76 3,5-dimethyl-1H- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z) bondnaphthalen-1-yl 3.73^([b]) pyrazol-1-yl I-77 3,5-dimethyl-1H- CH₂ OCH₂CH₂ CH₂CH₂ H CH═CH (E) bond naphthalen-1-yl 3.58^([b]) pyrazol-1-ylI-78 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ Br CH₂CH₂ bond phenyl 4.71^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-79 3,5-dimethyl-1H- CH₂ O CH₂CH₂CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl 3.39^([c]) pyrazol-1-yl I-805-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ CH₂CHCH₃ phenyl 4.77^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-81 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H CH₂CH₂ bond naphthalen-1-yl 4.37^([b]) (trifluoromethyl)-1H-pyrazol-1-yl I-82 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondpyridin-3-yl (trifluoromethyl)-1H- pyrazol-1-yl I-83 3,5-dimethyl-1H-CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ CH₂CHCH₃ phenyl 3.83^([b]) pyrazol-1-ylI-84 3,5-dimethyl-1H- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (E) bond phenyl3.04^([b]) pyrazol-1-yl I-85 3,5-dimethyl-1H- CH₂ O CH₂CH₂ CH₂CH₂ HCH═CH (E) CH₂CHCH₃ phenyl 3.83^([c]) pyrazol-1-yl I-86 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H C≡C bond H 2.57^([b]) (trifluoromethyl)-1H- pyrazol-1-ylI-87 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondnaphthalen-1-yl I-88 2,5-dibromophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondnaphthalen-1-yl I-89 5-iodo-2-methylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂bond naphtbalen-1-yl I-90 3-chloro-5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondphenyl (trifluoromethyl) pyridin-2-yl I-91 3-chloro-5- CH₂ O CH₂CH₂CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl (trifluoromethyl) pyridin-2-yl I-925-methyl-3- CH₂ S CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl(trifluoromethyl)-1H- pyrazol-1-yl I-93 5-methyl-3- CH₂ S CH₂CH₂ CH₂CH₂H CH═CH (E) bond phenyl 4.65^([b]) (trifluoromethyl)-1H- pyrazol-1-ylI-94 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (E) bond3-(trifluoromethyl)- 4.46^([b]) (trifluoromethyl)-1H- phenylpyrazol-1-yl I-95 1,3-benzodioxol-5-yl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondphenyl I-96 3,5-dimethyl-1H- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (E) bond3-(trifluoromethyl)- 3.56^([b]) pyrazol-1-yl phenyl I-972,3,6-trifluorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond naphthalen-1-yl4.71^([b]) I-98 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bondtrimethylsilyl 4.28^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-995-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond phenyl 3.82^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-100 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H C≡C bond 4-methoxyphenyl 3.79^([b]) (trifluoromethyl)-1H- pyrazol-1-ylI-101 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2-chlorophenyl4.12^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-102 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H C≡C bond 4-chlorophenyl 4.37^([b]) (trifluoromethyl)-1H-pyrazol-1-yl I-103 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond2-methoxyphenyl 3.67^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-1045-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2,4-dimethoxyphenyl3.67^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-105 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H C≡C bond 2,4-dichlorophenyl 4.72^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-106 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H C≡C bond 2,5-dimethoxyphenyl 3.65^([b]) (trifluoromethyl)-1H-pyrazol-1-yl I-107 3,5-diethyl-1H- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondnaphthalen-1-yl 4.04^([b]) pyrazol-1-yl I-108 5-ethyl-3- CH₂ O CH₂CH₂CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl 4.65^([b]) (trifluoromethyl)-1H-pyrazol-1-yl I-109 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondnaphthalen-1-yl 4.25^([b]) bis(difluoromethyl)- 1H-pyrazol-1-yl I-1103-tert-butyl-5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl5.36^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-111 5-tert-butyl-3- CH₂O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl 5.14^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-112 3-tert-butyl-5- CH₂ O CH₂CH₂CH₂CH₂ H CH₂CH₂ bond naphthalen-1-yl 5.78^([b]) (pentafluoroethyl)-1H-pyrazol-1-yl I-113 5-tert-butyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondnaphthalen-1-yl 5.54^([b]) (pentafluoroethyl)-1H- pyrazol-1-yl I-1143,5- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond naphthalen-1-yl 5.03^([b])bis(trifluoromethyl)- 1H-pyrazol-1-yl I-115 3,5-diethyl-1H- CH₂ O CH₂CH₂CH₂CH₂ H C≡C bond naphthalen-1-yl 4.2^([b]) pyrazol-1-yl I-1165-ethyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond naphthalen-1-yl 4.8^([b])(trifluoromethyl)- 1H-pyrazol-1-yl I-117 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H C≡Cbond naphthalen-1-yl 4.41^([b]) bis(difluoromethyl)- 1H-pyrazol-1-ylI-118 3-tert-butyl-5- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond naphthalen-1-yl5.48^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-119 5-tert-butyl-3- CH₂O CH₂CH₂ CH₂CH₂ H C≡C bond naphthalen-1-yl 5.14^([b])(trifluoromethyl)-1H- pyrazol-1-yl I-120 5-tert-butyl-3- CH₂ O CH₂CH₂CH₂CH₂ H C≡C bond naphthalen-1-yl 5.59^([b]) (pentafluoroethyl)-1H-pyrazol-1-yl I-121 3-(propan-2-yl)-5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondnaphthalen-1-yl 4.89^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-1223-(propan-2-yl)-5- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond naphthalen-1-yl4.99^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-123 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2,4-dichlorophenyl 477^([c]);(trifluoromethyl)-1H- 4.74^([b]) pyrazol-1-yl I-124 2,5-dibromophenylCH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond naphthalen-1-yl 5.52^([c]); 5.47^([b])I-125 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond H 3.08^([b])I-126 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2-methylphenyl4.16^([c]); (trifluoromethyl)-1H- 4.08^([b]) pyrazol-1-yl I-1275-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2-bromophenyl(trifluoromethyl)-1H- pyrazol-1-yl I-128 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H CH₂CH₂ bond 2,6-difluorophenyl 3.97^([c],) (trifluoromethyl)-1H-3.9^([b]) pyrazol-1-yl I-129 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂bond quinolin-8-yl (trifluoromethyl)-1H- pyrazol-1-yl I-130 5-methyl-3-CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 3-methylpyridin-2-yl(trifluoromethyl)-1H- pyrazol-1-yl I-131 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂H CH₂CH₂ bond 3,5-dimethylisoxazol- (trifluoromethyl)-1H- 4-ylpyrazol-1-yl I-132 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondcyclohexyl 5.01^([b]) (trifluoromethyl)-1H- pyrazol-1-yl I-1335-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 1,2,3,4- 4.95^([b])(trifluoromethyl)-1H- tetrahydronaphthalen- pyrazol-1-yl 1-yl I-134 3,5-CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2-methylphenyl bis(trifluoromethyl)-1H-pyrazol-1-yl I-135 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond2-bromophenyl bis(trifluoromethyl)- 1H-pyrazol-1-yl I-136 3,5- CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2,6-difluorophenyl bis(trifluoromethyl)-1H-pyrazol-1-yl I-137 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondquinolin-8-yl bis(trifluoromethyl)- 1H-pyrazol-1-yl I-138 3,5- CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 3-methylpyridin-2-yl bis(trifluoromethyl)-1H-pyrazol-1-yl I-139 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond3,5-dimethylisoxazol- bis(trifluoromethyl)- 4-yl 1H-pyrazol-1-yl I-1403,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond cyclohexyl 5.76^([b])bis(trifluoromethyl)- 1H-pyrazol-1-yl I-141 3,5- CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond 1,2,3,4- bis(trifluoromethyl)- tetrahydronaphthalen-1H-pyrazol-1-yl 1-yl I-142 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond2-methylphenyl bis(difluoromethyl)- 1H-pyrazol-1-yl I-143 3,5- CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2-bromophenyl bis(difluoromethyl)-1H-pyrazol-1-yl I-144 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond2,6-difluorophenyl bis(difluoromethyl)- 1H-pyrazol-1-yl I-145 3,5- CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond quinolin-8-yl bis(difluoromethyl)-1H-pyrazol-1-yl I-146 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond3-methylpyridin-2-yl bis(difluoromethyl)- 1H-pyrazol-1-yl I-147 3,5- CH₂O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 3,5-dimethylisoxazol- bis(difluoromethyl)-4-yl 1H-pyrazol-1-yl I-148 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bondcyclohexyl 4.87^([b]) bis(difluoromethyl)- 1H-pyrazol-1-yl I-149 3,5-CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 1,2,3,4- 4.78^([b])bis(difluoromethyl)- tetrahydronaphthalen- 1H-pyrazol-1-yl 1-yl I-1502,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2-methylphenylI-151 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2-bromophenylI-152 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond2,6-difluorophenyl I-153 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂bond quinolin-8-yl I-154 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂bond 3-methylpyridin-2-yl I-155 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond 3,5-dimethylisoxazol- 4-yl I-156 2,5-dichlorophenyl CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond cyclohexyl I-157 2,5-dichlorophenyl CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 1,2,3,4- tetrahydronaphthalen- 1-yl I-1582,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 2-methylphenyl4.77^([c]); 4.67^([b]) I-159 2,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond 2-bromophenyl I-160 2,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond 2,6-difluorophenyl 4.55^([c]); 4.48^([b]) I-1612,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond quinolin-8-yl I-1622,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH₂CH₂ bond3-methylpyridin-2-yl I-163 2,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ HCH₂CH₂ bond 3,5-dimethylisoxazol- 4-yl I-164 2,5-dimethylphenyl CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond cyclohexyl I-165 2,5-dimethylphenyl CH₂ OCH₂CH₂ CH₂CH₂ H CH₂CH₂ bond 1,2,3,4- tetrahydronaphthalen- 1-yl I-1665-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 2-methylphenyl 4.23^([b])(trifluoromethyl)-1H- (mixture of pyrazol-1-yl (Z) and (E) isomers)I-167 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 2-bromophenyl 4.39(trifluoromethyl)-1H- (mixture of and pyrazol-1-yl (Z) and (E)4.44^([b]) isomers) I-168 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond2,6-difluorophenyl 3.90 (trifluoromethyl)-1H- (mixture of andpyrazol-1-yl (Z) and (E) 4.21^([b]) isomers) I-169 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H CH═CH bond quinolin-8-yl (trifluoromethyl)-1H- (mixtureof pyrazol-1-yl (Z) and (E) isomers) I-170 5-methyl-3- CH₂ O CH₂CH₂CH₂CH₂ H CH═CH bond 3-methylpyridin-2-yl (trifluoromethyl)-1H- (mixtureof pyrazol-1-yl (Z) and (E) isomers) I-171 5-methyl-3- CH₂ O CH₂CH₂CH₂CH₂ H CH═CH bond 3,5-dimethylisoxazol- (trifluoromethyl)-1H- (mixtureof 4-yl pyrazol-1-yl (Z) and (E) isomers) I-172 5-methyl-3- CH₂ O CH₂CH₂CH₂CH₂ H CH═CH bond cyclohexyl 4.99 (trifluoromethyl)-1H- (mixture ofand pyrazol-1-yl (Z) and (E) 5.07^([b]) isomers) I-173 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H CH═CH bond 1,2,3,4- 4.02 (trifluoromethyl)-1H- (mixtureof tetrahydronaphthalen- and pyrazol-1-yl (Z) and (E) 1-yl 4.10^([b])isomers) I-174 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 2-methylphenyl4.93^([b]) bis(trifluoromethyl)- (mixture of 1H-pyrazol-1-yl (Z) and (E)isomers) I-175 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 2-bromophenyl4.99^([b]) bis(trifluoromethyl)- (mixture of 1H-pyrazol-1-yl (Z) and (E)isomers) I-176 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 2,6-difluorophenyl4.88^([b]) bis(trifluoromethyl)- (mixture of 1H-pyrazol-1-yl (Z) and (E)isomers) I-177 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond quinolin-8-ylbis(trifluoromethyl)- (mixture of 1H-pyrazol-1-yl (Z) and (E) isomers)I-178 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 3-methylpyridin-2-ylbis(trifluoromethyl)- (mixture of 1H-pyrazol-1-yl (Z) and (E) isomers)I-179 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 3,5-dimethylisoxazol-bis(trifluoromethyl)- (mixture of 4-yl 1H-pyrazol-1-yl (Z) and (E)isomers) I-180 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond cyclohexyl 5.59bis(trifluoromethyl)- (mixture of and 1H-pyrazol-1-yl (Z) and (E)5.68^([b]) isomers) I-181 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 1,2,3,4-5.60 bis(trifluoromethyl)- (mixture of tetrahydronaphthalen- and1H-pyrazol-1-yl (Z) and (E) 1-yl 5.78^([b]) isomers) I-182 3,5- CH₂ OCH₂CH₂ CH₂CH₂ H CH═CH bond 2-methylphenyl bis(difluoromethyl)- (mixtureof 1H-pyrazol-1-yl (Z) and (E) isomers) I-183 3,5- CH₂ O CH₂CH₂ CH₂CH₂ HCH═CH bond 2-bromophenyl 4.25 bis(difluoromethyl)- (mixture of and1H-pyrazol-1-yl (Z) and (E) 4.29^([b]) isomers) I-184 3,5- CH₂ O CH₂CH₂CH₂CH₂ H CH═CH bond 2,6-difluorophenyl 3.74 bis(difluoromethyl)-(mixture of and 1H-pyrazol-1-yl (Z) and (E) 4.05^([b]) isomers) I-1853,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond quinolin-8-yl bis(difluoromethyl)-(mixture of 1H-pyrazol-1-yl (Z) and (E) isomers) I-186 3,5- CH₂ O CH₂CH₂CH₂CH₂ H CH═CH bond 3-methylpyridin-2-yl bis(difluoromethyl)- (mixtureof 1H-pyrazol-1-yl (Z) and (E) isomers) I-187 3,5- CH₂ O CH₂CH₂ CH₂CH₂ HCH═CH bond 3,5-dimethylisoxazol- bis(difluoromethyl)- (mixture of 4-yl1H-pyrazol-1-yl (Z) and (E) isomers) I-188 3,5- CH₂ O CH₂CH₂ CH₂CH₂ HCH═CH bond cyclohexyl 4.79 bis(difluoromethyl)- (mixture of and1H-pyrazol-1-yl (Z) and (E) 4.85^([b]) isomers) I-189 3,5- CH₂ O CH₂CH₂CH₂CH₂ H CH═CH bond 1,2,3,4- 4.81 bis(difluoromethyl)- (mixture oftetrahydronaphthalen- and 1H-pyrazol-1-yl (Z) and (E) 1-yl 4.97^([b])isomers) I-190 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond2-methylphenyl (mixture of (Z) and (E) isomers) I-191 2,5-dichlorophenylCH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 2-bromophenyl (mixture of (Z) and (E)isomers) I-192 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond2,6-difluorophenyl (mixture of (Z) and (E) isomers) I-1932,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond quinolin-8-yl(mixture of (Z) and (E) isomers) I-194 2,5-dichlorophenyl CH₂ O CH₂CH₂CH₂CH₂ H CH═CH bond 3-methylpyridin-2-yl (mixture of (Z) and (E)isomers) I-195 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond3,5-dimethylisoxazol- (mixture of 4-yl (Z) and (E) isomers) I-1962,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond cyclohexyl (mixtureof (Z) and (E) isomers) I-197 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ HCH═CH bond 1,2,3,4- (mixture of tetrahydronaphthalen- (Z) and (E) 1-ylisomers) I-198 2,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond2-methylphenyl (mixture of (Z) and (E) isomers) I-199 2,5-dimethylphenylCH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 2-bromophenyl (mixture of (Z) and (E)isomers) I-200 2,5-dimethylpbenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond2,6-difluorophenyl (mixture of (Z) and (E) isomers) I-2012,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond quinolin-8-yl(mixture of (Z) and (E) isomers) I-202 2,5-dimethylphenyl CH₂ O CH₂CH₂CH₂CH₂ H CH═CH bond 3-methylpyridin-2-yl (mixture of (Z) and (E)isomers) I-203 2,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond3,5-dimethylisoxazol- (mixture of 4-yl (Z) and (E) isomers) I-2042,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond cyclohexyl (mixtureof (Z) and (E) isomers) I-205 2,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ HCH═CH bond 1,2,3,4- (mixture of tetrahydronaphthalen- (Z) and (E) 1-ylisomers) I-206 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2-methylphenyl4.15^([c]); (trifluoromethyl)-1H- 4.15^([b]) pyrazol-1-yl I-2075-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2-bromophenyl 4.19^([c]);(trifluoromethyl)-1H- 4.16^([b]) pyrazol-1-yl I-208 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H C≡C bond 2,6-difluorophenyl 3.86^([c]);(trifluoromethyl)-1H- 3.83^([b]) pyrazol-1-yl I-209 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H C≡C bond quinolin-8-yl (trifluoromethyl)-1H-pyrazol-1-yl I-210 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond3-methylpyridin-2-yl 2.95^([c]); (trifluoromethyl)-1H- 2.72^([b])pyrazol-1-yl I-211 5-methyl-3- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond3,5-dimethylisoxazol- (trifluoromethyl)-1H- 4-yl pyrazol-1-yl I-212 3,5-CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2-methylphenyl 4.73^([b])bis(trifluoromethyl)- 1H-pyrazol-1-yl I-213 3,5- CH₂ O CH₂CH₂ CH₂CH₂ HC≡C bond 2-bromophenyl 4.74^([b]) bis(trifluoromethyl)- 1H-pyrazol-1-ylI-214 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2,6-difluorophenyl 4.4^([b])bis(trifluoromethyl)- 1H-pyrazol-1-yl I-215 3,5- CH₂ O CH₂CH₂ CH₂CH₂ HC≡C bond quinolin-8-yl bis(trifluoromethyl)- 1H-pyrazol-1-yl I-216 3,5-CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 3-methylpyridin-2-yl 3.37^([b])bis(trifluoromethyl)- 1H-pyrazol-1-yl I-217 3,5- CH₂ O CH₂CH₂ CH₂CH₂ HC≡C bond 3,5-dimethylisoxazol- bis(trifluoromethyl)- 4-yl1H-pyrazol-1-yl I-218 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2-methylphenyl4.02^([c]); bis(difluoromethyl)- 3.99^([b]) 1H-pyrazol-1-yl I-219 3,5-CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2-bromophenyl 4.04^([c]);bis(difluoromethyl)- 4.04^([b]) 1H-pyrazol-1-yl I-220 3,5- CH₂ O CH₂CH₂CH₂CH₂ H C≡C bond 2,6-difluorophenyl 3.73^([c]); bis(difluoromethyl)-3.7^([b]) 1H-pyrazol-1-yl I-221 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bondquinolin-8-yl bis(difluoromethyl)- 1H-pyrazol-1-yl I-222 3,5- CH₂ OCH₂CH₂ CH₂CH₂ H C≡C bond 3-methylpyridin-2-yl 2.86^([c]);bis(difluoromethyl)- 2.68^([b]) 1H-pyrazol-1-yl I-223 3,5- CH₂ O CH₂CH₂CH₂CH₂ H C≡C bond 3,5-dimethylisoxazol- 3.09^([b]) bis(difluoromethyl)-4-yl 1H-pyrazol-1-yl I-224 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡Cbond 2-methylphenyl 4.91^([b]) I-225 2,5-dichlorophenyl CH₂ O CH₂CH₂CH₂CH₂ H C≡C bond 2-bromophenyl 4.91^([b]) I-226 2,5-dichlorophenyl CH₂O CH₂CH₂ CH₂CH₂ H C≡C bond 2,6-difluorophenyl 4.52^([b]) I-2272,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond quinolin-8-yl I-2282,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 3-methylpyridin-2-yl3.55^([c]) 3.35^([b]) I-229 2,5-dichlorophenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡Cbond 3,5-dimethylisoxazol- 3.86^([b]) 4-yl I-230 2,5-dimethylphenyl CH₂O CH₂CH₂ CH₂CH₂ H C≡C bond 2-methylphenyl 4.78^([c]); 4.75^([b]) I-2312,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 2-bromophenyl4.8^([c]); 4.77^([b]) I-232 2,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡Cbond 2,6-difluorophenyl 4.39^([c]); 4.36^([b]) I-233 2,5-dimethylphenylCH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond quinolin-8-yl I-234 2,5-dimethylphenylCH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 3-methylpyridin-2-yl I-2352,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H C≡C bond 3,5-dimethylisoxazol-3.71^([c]); 4-yl 3.67^([b]) I-236 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z)bond 3-methylpyridin-2-yl 2.46^([b]) bis(trifluoromethyl)-1H-pyrazol-1-yl I-237 2,5-dimethylphenyl CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH (Z)bond 2-methylphenyl 4.95^([c]); 4.86^([b]) I-238 2,5-dimethylphenyl CH₂O CH₂CH₂ CH₂CH₂ H C≡C bond H 2.93^([b]); 2.95^([c]) I-239 3,5- CH₂ OCH₂CH₂ CH₂CH₂ H C≡C bond H 2.45^([b]) bis(difluoromethyl)-1H-pyrazol-1-yl I-240 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CH bond 2-chloro-6-4.85 bis(trifluoromethyl)- (mixture of fluorophenyl and 1H-pyrazol-1-yl(Z) and (E) 5.09^([b]) isomers) I-241 3,5- CH₂ O CH₂CH₂ CH₂CH₂ H CH═CHbond 2-chloro-6- 4.09 bis(difluoromethyl)- (mixture of fluorophenyl and1H-pyrazol-1-yl (Z) and (E) 4.33^([b]) isomers) I-242 5-methyl-3- CH₂ OCH₂CH₂ CH₂CH₂ H CH═CH bond 2-chloro-6- 4.48^([b]) (trifluoromethyl)-1H-(mixture of fluorophenyl pyrazol-1-yl (Z) and (E) isomers) The logPvalues were determined in accordance with EEC Directive 79/831 AnnexV.A8 by HPLC (High Performance Liquid Chromatography) on reversed-phasecolumns (C 18), using the methods below: ^([a])The determination wascarried out in the acidic range at pH 2.3 using the mobile phases 0.1%aqueous phosphoric acid and acetonitrile; linear gradient from 10%acetonitrile to 95% acetonitrile. ^([b])The LC-MS determination in theacidic range was carried out at pH 2.7 using the mobile phases 0.1%aqueous formic acid and acetonitrile (contains 0.1% formic acid): lineargradient from 10% acetonitrile to 95% acetonitrile. ^([c])The LC-MSdetermination in the neutral range was carried out at pH 7.8 using themobile phases 0.001 molar aqueous ammonium bicarbonate solution andacetonitrile; linear gradient from 10% acetonitrile to 95% acetonitrile.Calibration was carried out using unbranched alkan-2-ones (having 3 to16 carbon atoms), with known logP values (determination of the logPvalues by the retention times using linear interpolation between twosuccessive alkanones). The lambda-max values were determined in themaxima of the chromatographic signals using the UV spectra from 200 nmto 400 nm.

NMR Data of Selected Examples

Ex NMR Data I-1 ¹HNMR δ = 7.46 (m, 2H), 7.31-7.18 (m, 4H), 6.62 (d, 1H),6.57 (d, 1H), 6.44 (s, 1H), 5.19 (bs, 2H), 4.20 (bs, 1H), 3.90 (bs, 1H),3.26 (m, 2H), 2.90 (m, 1H), 2.21 (s, 3H), 2.05 (m, 2H), 1.80-1.50 (m,2H) ppm I-2 ¹HNMR δ = 7.95-7.92 (m, 2H), 7.87-7.84 (m, 1H), 7.52-7.43(m, 4H), 7.11 (d, 1H), 6.93 (d, 1H), 6.88 (s, 1H), 6.45 (s, 1H), 5.14(s, 2H), 4.05 (bs, 1H), 3.74 (bs, 1H), 3.20-3.05 (m, 2H), 2.88 (bs, 1H),2.24 (s, 3H), 1.90-1.78 (bs, 2H), 1.50 (bs, 1H), 1.35 (bs, 1H) ppm I-3¹HNMR δ = 7.32 (s, 1H), 7.29-7.22 (m, 4H), 7.15 (m, 1H), 6.44 (s, 1H),6.35 (d, 1H), 5.60 (m, 1H), 5.20 (bs, 2H), 4.30 (bs, 1H), 3.98 (bs, 1H),3.38-3.25 (m, 2H), 3.05-2.84 (m, 4H), 2.22 (s, 3H), 2.17-2.05 (m, 2H),1.85-1.56 (m, 2H), 1.26 (d, 3H) ppm I-26 ¹HNMR δ = 7.56 (d, 2H), 7.50(s, 1H), 7.39-7.34 (m, 3H), 7.28-7.18 (m, 2H), 6.45 (s, 1H), 5.23 (bs,2H), 4.37 (bs, 1H), 4.01 (bs, 1H), 3.35 (m, 1H), 3.32 (bs, 1H), 2.90(bs, 1H), 2.23 (s, 3H), 2.18-2.10 (m, 2H), 1.80 (bs, 1H), 1.63 (bs, 1H)ppm I-27 ¹HNMR δ = 8.23 (d, 1H), 8.16 (d, 1H), 7.95 (d, 1H), 7.88 (d,1H), 7.83 (d, 1H), 7.64 (s, 1H), 7.63-7.51 (m, 3H), 7.27 (d, 1H), 6.46(s, 1H), 5.24 (bs, 2H), 4.38 (bs, 1H), 4.03 (bs, 1H), 3.40 (m, 1H), 3.32(bs, 1H), 2.94 (bs, 1H), 2.24 (s, 3H), 2.23-2.12 (m, 2H), 1.85 (bs, 1H),1.70 (bs, 1H) ppm I-50 ¹HNMR (CD₃CN) δ = 8.39 (d, 1H), 7.96 (d, 2H),7.80 (d, 1H), 7.72 (s, 1H), 7.67-7.50 (m, 3H), 6.37 (s, 1H), 5.05 (s,2H), 4.45 (bs, 1H), 3.98 (bs, 1H), 3.40-3.20 (m, 2H), 2.93 (bs, 1H),2.25 (s, 3H), 2.25-2.15 (m, 2H), 1.90-1.75 (m, 2H) ppm I-51 ¹HNMR(CD₃CN) δ = 8.74 (dd, 1H), 8.59 (dd, 1H), 7.99 (s, 1H), 7.96 (m, 1H),7.45 (dd, 1H), 6.45 (s, 1H), 5.22 (bs, 2H), 4.35 (bs, 1H), 4.00 (bs,1H), 3.40-3.20 (m, 3H), 2.22 (s, 3H), 2.17-2.10 (m, 2H), 1.90-1.55 (m,2H) ppm I-52 ¹HNMR (CD₃CN) δ = 7.46 (s, 1H), 7.42-7.34 (m, 4H),7.30-7.25 (m, 1H), 6.39 (s, 1H), 5.09 (d, 1H), 5.02 (d, 1H), 4.45 (d,1H), 3.91 (d, 1H), 3.84 (s, 2H), 3.25 (m, 2H), 2.82 (t, 1H), 2.23 (s,3H), 2.18-2.05 (m, 2H), 1.82 (qd, 1H), 1.66 (qd, 1H) ppm I-53 ¹HNMR δ =7.28-7.26 (m, 2H), 7.22-7.21 (m, 2H), 7.19-7.15 (m, 2H), 6.51 (s, 1H),5.33 (d, 1H), 5.25 (d, 1H), 4.36 (d, 1H), 3.95 (d, 1H), 3.35-3.20 (m,2H), 2.96 (s, 4H), 2.82 (t, 1H), 2.21 (s, 3H), 2.09 (d, 1H), 2.07 (d,1H), 1.78 (m, 1H), 1.53 (m, 1H) ppm I-54 ¹HNMR δ = 7.26-7.13 (m, 5H),7.06 (s, 1H), 5.77 (s, 1H), 4.91 (bs, 2H), 4.28 (m, 1H), 4.03 (m, 1H),3.25 (m, 1H), 3.16 (m, 1H), 2.97 (m, 4H), 2.85 (m, 1H), 2.11 (s, 3H),2.10-1.97 (m + s, 5H), 1.61 (m, 2H) ppm I-55 ¹HNMR δ = 7.85 (d, 1H),7.26-7.13 (m, 5H), 7.06 (s, 1H), 6.66 (d, 1H), 5.27 (bs, 2H), 4.30 (bs,1H), 3.95 (bs, 1H), 3.26 (m, 1H), 3.20-2.80 (m + s, 6H), 2.07 (m, 2H),1.80-1.50 (m, 2H) ppm I-57 ¹HNMR δ = 7.34-7.12 (m, 9H), 7.04 (s, 1H),4.38 (bs, 1H), 4.00 (bs, 1H), 3.75 (s, 2H), 3.27-2.98 (m, 2H), 2.96 (m,4H), 2.80 (bs, 1H), 2.02 (m, 2H), 1.51 (m, 2H) ppm I-58 ¹HNMR δ =7.27-7.21 (m, 2H), 7.20-7.14 (m, 3H), 7.05 (s, 1H), 4.37 (bs, 1H), 3.95(bs, 1H), 3.26-3.18 (m, 2H), 2.96 (s, 4H), 2.80 (bs, 1H), 2.33 (t, 2H),2.04 (d, 2H), 1.55 (bs, 2H), 1.50 (tt, 2H), 1.33 (tq, 2H), 0.90 (t, 3H)ppm I-59 ¹HNMR δ = 7.47 (s, 1H), 7.26-7.13 (m, 5H), 7.07 (s, 1H), 5.46(m, 2H), 4.27 (bs, 1H), 3.93 (bs, 1H), 3.30 (m, 1H), 3.20-2.85 (m + s,6H), 2.05 (m, 2H), 1.79 (bs, 1H), 1.57 (bs, 1H) ppm I-60 ¹HNMR δ =7.26-7.13 (m, 5H), 7.07 (s, 1H), 5.29 (bs, 2H), 4.30 (bs, 1H), 3.92 (bs,1H), 3.28 (m, 1H), 3.20 (m, 1H), 3.00-2.80 (m, 5H), 2.20 (s, 3H), 2.07(m, 2H), 1.80 (bs, 1H), 1.60 (bs, 1H) ppm I-61 ¹HNMR δ = 8.07-7.90 (m,3H), 7.26-7.21 (m, 2H), 7.20-7.14 (m, 3H), 7.08 (s, 1H), 4.50 (d, 1H),3.35-3.23 (m, 4H), 2.97 (s, 4H), 2.22-2.10 (m, 1H), 2.00-1.87 (m, 2H),1.87-1.45 (m, 2H) ppm I-63 ¹HNMR δ = 7.44-7.43 (m, 1H), 7.28-7.12 (m,6H), 7.05 (s, 1H), 6.99 (d, 1H), 4.38 (bs, 1H), 3.99 (bs, 1H), 3.72 (s,2H), 3.22-3.15 (m, 2H), 2.96 (s, 4H), 2.81 (bs, 1H), 2.00 (d, 2H), 1.52(m, 2H) ppm I-64 ¹HNMR δ = 7.26-7.21 (m, 2H), 7.20-7.13 (m, 3H), 7.06(s, 1H), 5.70 (m, 1H), 4.30 (bs, 1H), 4.00 (bs, 1H), 3.30-3.19 (m, 2H),2.96 (s, 5H), 2.26 (d, 3H), 2.08-1.96 (m, 2H), 1.64-1.54 (m, 5H) ppmI-65 ¹HNMR δ = 7.40 (s, 1H), 7.26-7.15 (m, 5H), 7.06 (s, 1H), 4.35 (bs,1H), 4.05 (bs, 1H), 3.76 (s, 3H), 3.49 (s, 2H), 3.30-3.19 (m, 2H), 2.99(s, 4H), 2.82 (bs, 1H), 2.08-2.00 (m, 2H), 1.58 (bs, 2H) ppm I-66 ¹HNMRδ = 7.26-7.21 (m, 2H), 7.20-7.12 (m, 3H), 7.05 (s, 1H), 6.85-6.80 (m,3H), 6.75-6.71 (dd, 1H), 3.93 (bs, 1H), 3.74 (s, 3H), 3.69 (s, 3H), 3.20(m, 1H), 2.96 (s, 4H), 2.80-2.74 (m, 2H), 2.65-2.55 (bs, 2H), 2.04-1.97(m, 2H), 1.58-1.42 (m, 2H), 1.28 (t, 2H) ppm I-67 ¹HNMR δ = 7.71-7.58(m, 3H), 7.27-7.12 (m, 5H), 7.07 (s, 1H), 4.37 (bs, 1H), 4.05 (bs, 1H),3.97 (s, 2H), 3.35-3.23 (m, 2H), 2.97 (s, 4H), 2.88 (bs, 1H), 2.07 (d,2H), 1.65 (bs, 2H) ppm I-68 ¹HNMR δ = 7.99 (d, 1H), 7.26-7.12 (m, 5H),7.05 (s, 1H), 6.69 (d, 1H), 5.74 (q, 1H), 4.40-3.95 (m, 2H), 3.24 (m,1H), 3.20-2.75 (m + s, 6H), 2.05 (m, 2H), 1.30-1.70 (m + d, 5H) ppm I-70¹HNMR (CD₃CN) δ = 8.10 (s, 1H), 7.71 (d, 1H), 7.60 (d, 1H), 7.29-7.15(m, 6H), 7.07 (dd, 1H), 6.87 (s, 1H), 5.45 (d, 1H), 5.36 (d, 1H), 4.48(d, 1H), 4.00 (d, 1H), 3.35-3.23 (m, 2H), 3.00 (s, 4H), 2.86 (t, 1H),2.18-2.06 (m, 2H), 1.80 (qd, 1H), 1.66 (qd, 1H) ppm I-71 ¹HNMR δ = 8.03(d, 1H), 7.93 (d, 1H), 7.47 (t, 1H), 7.40 (t, 1H), 7.25-7.16 (m, 5H),7.06 (s, 1H), 4.40 (bs, 1H), 4.34 (s, 2H), 4.09 (bs, 1H), 3.40-3.15 (m,3H), 2.96 (s, 4H), 2.08-2.02 (m, 2H), 1.65 (bs, 2H) ppm I-74 ¹HNMR δ =8.31 (d, 1H), 8.02 (d, 2H), 7.82 (d, 1H), 7.69 (t, 1H), 7.63-7.51 (m,3H), 5.79 (s, 1H), 4.95 (s, 2H), 3.41-3.32 (m, 2H), 2.19-2.09 (m, 3H),2.12 (s, 3H), 2.07 (s, 3H), 1.81-1.53 (m, 4H) ppm I-76 ¹HNMR δ = 8.21(d, 1H), 8.13 (d, 1H), 7.95 (d, 1H), 7.89 (d, 1H), 7.84 (d, 1H),7.62-7.51 (m, 4H), 7.28 (d, 1H), 5.79 (s, 1H), 4.92 (s, 1H), 3.42-3.31(m, 2H), 2.21-2.09 (m, 3H), 2.12 (s, 3H), 2.07 (s, 3H), 1.85-1.59 (m,4H) ppm I-77 ¹HNMR δ = 7.29 (dd, 2H), 7.85 (dd, 1H), 7.55-7.41 (m, 4H),7.11 (d, 1H), 6.90 (t, 2H), 5.79 (s, 1H), 4.86 (s, 2H), 3.10 (m, 1H),2.51 (m, 2H), 2.11 (s, 3H), 2.06 (s, 3H), 2.88-2.72 (m, 2H), 1.49-1.31(m, 4H) ppm I-78 ¹HNMR δ = 7.27-7.22 (m, 2H), 7.18-7.13 (m, 3H), 6.45(s, 1H), 5.22 (bs, 2H), 4.38 (bs, 1H), 3.95 (bs, 1H), 3.33-3.20 (m, 2H),2.94 (s, 4H), 2.93 (bs, 1H), 2.22 (s, 3H), 2.09-2.02 (m, 2H), 1.80-1.50(m, 2H) ppm I-79 ¹HNMR δ = 8.09 (d, 1H), 7.89 (d, 1H), 7.76 (d, 1H),7.56-7.43 (m, 2H), 7.41-7.32 (m, 2H), 7.11 (s, 1H), 5.78 (s, 1H), 4.92(s, 2H), 3.47-3.41 (m, 4H), 3.46-3.22 (m, 3H), 2.12 (s, 3H), 2.09-2.02(m, 2H), 2.06 (s, 3H), 1.77-1.49 (m, 4H) ppm I-80 ¹HNMR δ = 7.28-7.23(m, 2H), 7.19-7.14 (m, 3H), 7.02 (s, 1H), 6.44 (s, 1H), 5.20 (bs, 2H),4.30 (bs, 1H), 3.95 (bs, 1H), 3.30-3.20 (m, 2H), 2.87 (bs, 1H), 2.72 (m,1H), 2.67-2.62 (m, 2H), 2.22 (s, 3H), 2.07-2.02 (m, 2H), 1.72 (bs, 1H),1.63-1.47 (m, 5H), 1.19 (d, 3H) ppm I-81 ¹HNMR δ = 8.09 (d, 1H), 7.90(d, 1H), 7.75 (d, 1H), 7.56-7.46 (m, 2H), 7.42-7.33 (m, 2H), 7.12 (s,1H), 6.45 (s, 1H), 5.22 (bs, 2H), 4.31 (bs, 1H), 3.98 (bs, 1H), 3.44 (t,2H), 3.35-3.26 (m, 2H), 3.15-3.05 (m, 2H), 2.90 (bs, 1H), 2.23 (s, 3H),2.15-2.05 (m, 2H), 1.75 (bs, 1H), 1.62 (bs, 1H) ppm I-83 ¹HNMR δ =7.32-7.21 (m, 2H), 7.19-7.11 (m, 4H), 7.02 (s, 1H), 5.75 (s, 1H), 4.87(s, 1H), 3.26-3.12 (m, 2H), 2.72-2.68 (m, 2H), 2.67-2.59 (m, 4H), 2.11(s, 3H), 2.05 (s, 3H), 2.02-1.91 (m, 4H), 1.61-1.42 (m, 4H), 1.19 (d,3H) ppm I-84 ¹HNMR δ = 7.56 (d, 2H), 7.50 (s, 1H), 7.37 (d, 2H), 7.34(s, 1H), 7.30-7.16 (m, 2H), 5.79 (s, 1H), 4.93 (s, 2H), 3.41-3.26 (m,2H), 2.93-2.76 (m, 1H), 2.12 (s, 3H), 2.04 (s, 3H), 2.11-2.03 (m, 2H),1.78-1.54 (m, 4H) ppm I-85 ¹HNMR δ = 7.31-7.21 (m, 5H), 7.19-7.12 (m,1H), 6.33 (d, 1H), 5.79 (s, 1H), 5.62-5.52 (m, 1H), 4.92 (s, 2H),4.38-4.12 (m, 1H), 4.12-3.92 (m, 1H), 3.33-3.22 (m, 2H), 2.96-2.81 (m,4H), 2.10 (s, 3H), 2.03 (s, 3H), 1.72-1.53 (m, 4H), 1.21 (d, 3H) ppmI-86 ¹HNMR δ = 7.86 (s, 1H), 6.44 (s, 1H), 5.20 (bs, 2H), 4.31 (bs, 1H),4.08 (s, 1H), 3.98 (bs, 1H), 3.31 (m, 1H), 3.28 (bs, 1H), 2.88 (bs, 1H),2.22 (s, 3H), 2.13-2.05 (m, 2H), 1.78 (bs, 1H), 1.61 (bs, 1H) ppm I-93¹HNMR (CD₃CN) δ = 7.55 (d, 2H), 7.43 (d, 1H), 7.37 (t, 2H), 7.30-7.28(m, 2H), 7.18 (d, 1H), 6.39 (s, 1H), 5.41 (d, 1H), 5.26 (s, 2H), 4.42(d, 1H), 3.54 (t, 1H), 3.45 (m, 1H), 3.38 (t, 1H), 2.31 (s, 3H),2.30-2.23 (m, 2H), 1.95-1.80 (m, 2H) ppm I-94 ¹HNMR δ = 7.91 (s, 1H),7.72 (d, 1H), 7.61-7.49 (m, 2H), 7.47 (s, 1H), 6.65 (s, 1H), 6.44 (s,1H), 5.12 (s, 1H), 3.29-3.18 (m, 2H), 2.89-2.74 (m, 1H), 2.23-2.17 (m,2H), 2.20 (s, 3H), 2.01 (d, 2H), 1.72-1.61 (m, 2H), 1.61-1.49 (m, 2H)ppm I-96 ¹HNMR δ = 7.92 (s, 1H), 7.72 (d, 1H), 7.61-7.51 (m, 2H), 7.45(s, 1H), 6.64 (s, 1H), 5.78 (s, 1H), 4.85 (s, 1H), 3.28-3.12 (m, 2H),3.11-3.05 (m, 1H), 2.12-2.09 (m, 2H), 2.10 (s, 3H), 2.05 (s, 3H), 1.98(d, 2H), 1.63-1.48 (m, 4H) ppm I-97 ¹HNMR δ = 8.34 (d, 1H), 8.08 (s,1H), 8.01 (d, 2H), 7.83 (dd, 1H), 7.68 (m, 1H), 7.62 (m, 1H), 7.57 (dd,1H), 7.37 (m, 1H), 7.07 (m, 1H), 4.37 (bs, 1H), 4.15 (bs, 1H), 3.86 (bs,2H), 3.40 (m, 1H), 3.34 (bs, 1H), 2.88 (bs, 1H), 2.16 (bs, 2H), 1.78(bs, 1H), 1.64 (bs, 1H) ppm I-98 ¹HNMR δ = 7.70 (s, 1H), 6.27 (s, 1H),5.08 (d, 1H), 5.01 (d, 1H), 4.12 (bd, 1H), 3.76 (bd, 1H), 3.05 (t, 1H),2.59 (t, 1H), 1.97 (s, 3H), 1.88-1.77 (m, 2H), 1.56 (tdd, 1H), 1.30(tdd, 1H), 0.00 (s, 9H) ppm I-99 ¹HNMR δ = 7.92 (s, 1H), 7.57-7.54 (m,2H), 7.45-7.41 (m, 3H), 6.45 (s, 1H), 5.23 (bs, 2H), 4.33 (bs, 1H), 3.98(bs, 1H), 3.36 (m, 1H), 3.28 (bs, 1H), 2.89 (bs, 1H), 2.23 (s, 3H),2.16-2.08 (m, 2H), 1.80 (bs, 1H), 1.63 (bs, 1H) ppm I-100 ¹HNMR δ = 7.84(s, 1H), 7.49 (d, 2H), 6.98 (d, 2H), 6.45 (s, 1H), 5.22 (bs, 2H), 4.33(bs, 1H), 3.98 (bs, 1H), 3.80 (s, 3H), 3.34 (m, 1H), 3.28 (bs, 1H), 2.89(bs, 1H), 2.22 (s, 3H), 2.15-2.09 (m, 2H), 1.80 (bs, 1H), 1.63 (bs, 1H)ppm I-101 ¹HNMR δ = 7.99 (s, 1H), 7.67 (dd, 1H), 7.56 (dd, 1H), 7.45(td, 1H), 7.39 (td, 1H), 6.45 (s, 1H), 5.23 (bs, 2H), 4.33 (bs, 1H),3.98 (bs, 1H), 3.37 (m, 1H), 3.28 (bs, 1H), 2.89 (bs, 1H), 2.23 (s, 3H),2.15-2.09 (m, 2H), 1.80 (bs, 1H), 1.63 (bs, 1H) ppm I-102 ¹HNMR δ = 7.95(s, 1H), 7.60-7.55 (m, 2H), 7.52-7.46 (m, 2H), 6.45 (s, 1H), 5.22 (bs,2H), 4.33 (bs, 1H), 3.98 (bs, 1H), 3.35 (m, 1H), 3.28 (bs, 1H), 2.89(bs, 1H), 2.22 (s, 3H), 2.15-2.08 (m, 2H), 1.80 (bs, 1H), 1.63 (bs, 1H)ppm I-103 ¹HNMR δ = 7.86 (s, 1H), 7.47 (dd, 1H), 7.40 (td, 1H), 7.09 (d,1H), 6.98 (td, 1H), 6.45 (s, 1H), 5.23 (bs, 2H), 4.33 (bs, 1H), 3.98(bs, 1H), 3.86 (s, 3H), 3.35 (m, 1H), 3.29 (bs, 1H), 2.89 (bs, 1H), 2.23(s, 3H), 2.15-2.08 (m, 2H), 1.80 (bs, 1H), 1.63 (bs, 1H) ppm I-104 ¹HNMRδ = 7.81 (s, 1H), 7.38 (d, 1H), 6.63 (d, 1H), 6.56 (dd, 1H), 6.45 (s,1H), 5.22 (bs, 2H), 4.33 (bs, 1H), 3.98 (bs, 1H), 3.85 (s, 3H), 3.81 (s,3H), 3.34 (m, 1H), 3.29 (bs, 1H), 2.89 (bs, 1H), 2.22 (s, 3H), 2.15-2.07(m, 2H), 1.80 (bs, 1H), 1.64 (bs, 1H) ppm I-105 ¹HNMR (CD₃CN) δ = 7.67(s, 1H), 7.58 (d, 1H), 7.57 (d, 1H), 7.38 (dd, 1H), 6.37 (s, 1H), 5.04(bs, 2H), 4.46 (bs, 1H), 3.95 (bs, 1H), 3.33 (m, 1H), 3.29 (bs, 1H),2.90 (bs, 1H), 2.24 (s, 3H), 2.20-2.13 (m, 2H), 1.90-1.66 (m, 2H) ppmI-106 ¹HNMR δ = 7.87 (s, 1H), 7.04-6.95 (m, 3H), 6.45 (s, 1H), 5.22 (bs,2H), 4.33 (bs, 1H), 3.98 (bs, 1H), 3.81 (s, 3H), 3.74 (s, 3H), 3.34 (m,1H), 3.29 (bs, 1H), 2.89 (bs, 1H), 2.23 (s, 3H), 2.15-2.08 (m, 2H), 1.80(bs, 1H), 1.63 (bs, 1H) ppm I-123 ¹HNMR (CD₃CN) δ = 7.44 (d, 1H), 7.22(dd, 1H), 7.18 (d, 1H), 6.88 (s, 1H), 6.40 (s, 1H), 5.11 (d, 1H), 5.04(d, 1H), 4.45 (bd, 1H), 3.91 (bd, 1H), 3.27 (m, 1H), 3.09 (t, 2H), 3.00(t, 2H), 2.84 (td, 1H), 2.23 (s, 3H), 2.15 (bd, 1H), 2.10 (bd, 1H), 1.81(tdd, 1H), 1.63 (tdd, 1H) ppm I-124 ¹HNMR (CD₃CN) δ = 8.40 (d, 1H), 7.98(d, 2H), 7.82 (dd, 1H), 7.76 (s, 1H), 7.68 (m, 1H), 7.62 (m, 1H),7.56-7.45 (m, 3H), 7.33 (dd, 1H), 4.45 (bd, 1H), 4.06 (bd, 1H), 3.88 (d,1H), 3.81 (d, 1H), 3.36 (m, 1H), 3.30 (t, 1H), 2.84 (t, 1H), 2.25-2.10(m, 2H), 1.84 (m, 1H), 1.70 (m, 1H) ppm I-125 ¹HNMR δ = 7.93 (s, 1H),7.46-7.40 (m, 2H), 7.36 (d, 1H), 4.45-4.35 (m, 1H), 4.23 (s, 1H),4.11-4.02 (m, 1H), 3.87 (d, 2H), 2.88-2.72 (m, 1H), 2.15-2.00 (m, 2H),1.79-1.66 (m, 1H), 1.60-1.46 (m, 1H) I-126 ¹HNMR (CD₃CN) δ = 7.16-7.05(m, 4H), 6.87 (s, 1H), 6.39 (s, 1H), 5.11 (d, 1H), 5.03 (d, 1H), 4.46(d, 1H), 3.91 (d, 1H), 3.32-3.23 (m, 2H), 3.01-2.93 (m, 4H), 2.84 (t,1H), 2.27 (s, 3H), 2.23 (s, 3H), 2.18-2.07 (m, 2H), 1.82 (tdd, 1H), 1.65(tdd, 1H) I-128 ¹HNMR (CD₃CN) δ = 7.28-7.19 (m, 1H), 6.96-6.88 (m, 3H),6.39 (s, 1H), 5.10 (d, 1H), 5.03 (d, 1H), 4.43 (d, 1H), 3.90 (d, 1H),3.32-3.19 (m, 2H), 3.07-2.94 (m, 4H), 2.88 (td, 1H), 2.23 (s, 3H),2.16-2.03 (m, 2H), 1.79 (tdd, 1H), 1.62 (tdd, 1H) I-132 ¹HNMR δ = 7.12(s, 1H), 6.49 (s, 1H), 5.31 (d, 1H), 5.22 (d, 1H), 4.35 (d, 1H), 3.95(d, 1H), 3.45-3.20 (m, 2H), 2.82 (dd, 1H), 2.67 (dd, 2H), 2.21 (s, 3H),2.06 (dd, 2H), 1.80-1.49 (m, 8H), 1.30-1.09 (m, 5H), 0.98-0.85 (m, 2H)ppm I-133 ¹HNMR (CD₃CN) δ = 7.16-7.12 (m, 1H), 7.11-7.02 (m, 3H), 6.93(s, 1H), 6.38 (s, 1H), 5.08 (d, 1H), 5.01 (d, 1H), 4.45 (bd, 1H), 3.99(bd, 1H), 3.28-3.18 (m, 2H), 2.86-2.65 (m, 5H), 2.21 (s, 3H), 2.17-2.03(m, 3H), 1.94-1.57 (m, 8H) ppm I-134 ¹HNMR (CD₃CN) δ = 7.17 (s, 1H),7.14-7.07 (m, 4H), 6.88 (s, 1H), 5.35 (d, 1H), 5.28 (d, 1H), 4.43 (d,1H), 3.86 (d, 1H), 3.31-3.24 (m, 2H), 3.00-2.95 (m, 4H), 2.86 (ddd, 1H),2.27 (s, 3H), 2.16 (d, 1H), 2.10 (d, 1H), 1.82 (tdd, 1H), 1.65 (tdd, 1H)ppm I-136 ¹HNMR (CD₃CN) δ = 7.21 (m, 1H), 7.17 (s, 1H), 6.94-6.86 (m,3H), 5.34 (d, 1H), 5.28 (d, 1H), 4.39 (d, 1H), 3.84 (d, 1H), 3.30-3.22(m, 2H), 3.02 (t, 2H), 2.97 (t, 2H), 2.87 (ddd, 1H), 2.13 (d, 1H), 2.06(d, 1H), 1.79 (tdd, 1H), 1.61 (tdd, 1H) ppm I-138 ¹HNMR (CD₃CN) δ = 8.32(d, 1H), 7.44 (d, 1H), 7.17 (s, 1H), 7.06 (dd, 1H), 6.89 (s, 1H), 5.34(d, 1H), 5.28 (d, 1H), 4.42 (d, 1H), 3.85 (d, 1H), 3.30-3.23 (m, 2H),3.12 (s, 4H), 2.86 (ddd, 1H), 2.23 (s, 3H), 2.15 (d, 1H), 2.09 (d, 1H),1.80 (tdd, 1H), 1.62 (tdd, 1H) ppm I-140 ¹HNMR (CD₃CN) δ = 7.17 (s, 1H),6.90 (s, 1H), 5.35 (d, 1H), 5.27 (d, 1H), 4.42 (d, 1H), 3.86 (d, 1H),3.32-3.21 (m, 2H), 2.86 (ddd, 1H), 2.75-2.67 (m, 2H), 2.20-2.04 (m, 2H),1.85-1.50 (m, 9H), 1.42-1.12 (m, 4H), 1.00-0.88 (m, 2H) ppm I-148 ¹HNMRδ = 7.18 (t, 1H), 7.13 (t, 1H), 7.03 (t, 1H), 6.91 (s, 1H), 5.43 (d,1H), 5.35 (s, 1H), 4.32 (d, 1H), 3.94 (d, 1H), 3.30-3.21 (m, 2H), 2.82(dd, 1H), 2.67 (dd, 2H), 2.10-2.00 (m, 2H), 1.83-1.48 (m, 8H), 1.35-1.10(m, 5H), 0.95-0.85 (m, 2H) ppm I-149 ¹HNMR (CD₃CN) δ = 7.17-7.10 (m,1H), 7.11-7.03 (m, 3H), 6.95 (s, 1H), 6.89 (t, 1H), 6.82 (s, 1H), 6.78(t, 1H), 5.23 (d, 1H), 5.17 (d, 1H), 4.44 (bd, 1H), 3.88 (bd, 1H),3.30-3.21 (m, 2H), 2.98-2.67 (m, 5H), 2.15-2.03 (m, 3H), 1.94-1.58 (m,8H) ppm I-158 ¹HNMR δ = 7.18-7.05 (m, 5H), 7.03 (d, 1H), 6.93 (d, 1H),6.90 (s, 1H), 4.47 (d, 1H), 3.94 (d, 1H), 3.70 (d, 1H), 3.62 (d, 1H),3.35-3.22 (m, 2H), 2.95-2.85 (m, 4H), 2.78 (t, 1H), 2.25 (s, 3H), 2.23(s, 3H), 2.15 (s, 3H), 2.10-1.94 (m, 2H), 1.61-1.45 (m, 2H) I-160 ¹HNMR(CD₃CN) δ = 7.28-7.17 (m, 1H), 7.05 (d, 1H), 6.96 (d, 1H), 6.95-6.85 (m,4H), 4.52 (d, 1H), 3.93 (d, 1H), 3.68 (d, 1H), 3.62 (d, 1H), 3.26-3.11(m, 2H), 3.06-2.92 (m, 4H), 2.79 (td, 1H), 2.26 (s, 3H), 2.18 (s, 3H),2.09-1.97 (m, 2H), 1.60 (qd, 2H) I-166 ¹HNMR δ = 7.65-7.54 (m, 2H),7.25-7.10 (m, 4H), 6.88 and 6.74 (s, 1H), 6.50 (s, 1H), 5.37-5.18 (m,2H), 4.40 and 4.20 (d, 1H), 4.00 and 3.85 (d, 1H), 3.42-3.18 (m, 2H),2.85 (dd, 1H), 2.38 and 2.20 (s, 3H), 2.22 and 2.20 (s, 3H), 2.19-2.10and 2.05-1.93 (m, 2H), 1.83 and 1.67 (tdd, 1H), 1.59 and 1.48 (tdd, 1H)ppm I-167 ¹HNMR δ = 7.86 (dd, 1H), 7.67-7.62 (m, 2H), 7.56 (dd, 1H),7.43 (dd, 1H), 7.27 (d, 1H), 7.23 (dd, 1H), 6.50 (s, 1H), 5.34 (d, 1H),5.24 (d, 1H), 4.40 (d, 1H), 3.99 (d, 1H), 3.45-3.20 (m, 2H), 2.83 (dd,1H), 2.20 (s, 3H), 2.18-2.08 (m, 2H), 1.82 (tdd, 1H), 1.58 (tdd, 1H) ppmI-172 ¹HNMR δ = 7.37 and 7.30 (s, 1H), 6.49 (s, 1H), 6.44 and 5.49 (dd,1H), 6.35 and 6.24 (d, 1H), 5.35-5.18 (m, 2H), 4.37 and 4.29 (d, 1H),3.95 (bs, 1H), 3.35-3.13 (m, 3H), 2.93 and 2.82 (dd, 1H), 2.21 (s, 3H),2.18-2.02 (m, 2H), 1.85-1.48 (m, 6H), 1.35-1.05 (m, 6H) ppm I-173 ¹HNMRδ = 7.51 and 7.34 (s, 1H), 7.13-7.04 (m, 4H), 6.54 and 5.67 (dd, 1H),6.48 and 6.47 (s, 1H), 6.45 and 6.38 (d, 1H), 5.30 and 5.29 (d, 1H),5.21 and 5.19 (d, 1H), 4.94 and 3.62 (m, 1H), 4.32 and 4.29 (d, 1H),3.94 (m, 1H), 3.36-3.20 (m, 2H), 2.92-2.73 (m, 3H), 2.20 and 2.18 (s,3H), 2.16-1.63 (m, 7H), 1.58 (m, 1H) ppm I-174 ¹HNMR δ = 7.65-7.55 (m,3H), 7.24-7.17 (m, 4H), 7.15 and 7.11 (s, 1H), 6.89 and 6.72 (s, 1H),5.65-5.46 (m, 2H), 4.37 and 4.16 (d, 1H), 3.98 and 3.82 (d, 1H),3.43-3.19 (m, 2H), 2.87 (dd, 1H), 2.38 and 2.20 (s, 3H), 2.18-2.10 and2.05-1.92 (m, 2H), 1.82 and 1.66 (tdd, 1H), 1.58 and 1.43 (tdd, 1H) ppmI-175 ¹HNMR δ = 7.84 (dd, 1H), 7.67-7.56 (m, 4H), 7.41 (t, 1H), 7.27 (d,1H), 7.23 (td, 1H), 5.62 (d, 1H), 5.50 (d, 1H), 4.37 (d, 1H), 3.98 (d,1H), 3.45-3.15 (m, 2H), 2.87 (dd, 1H), 2.18-2.09 (m, 2H), 1.82 (tdd,1H), 1.56 (tdd, 1H) ppm I-180 ¹HNMR (CD₃CN) δ = 7.17 (s, 1H), 7.13 and7.02 (s, 1H), 6.49 and 5.55 (dd, 1H), 6.37 and 6.23 (d, 1H), 5.34 (d,1H), 5.31 (d, 1H), 4.43 and 4.37 (d, 1H), 3.86 (d, 1H), 3.37-3.18 (m,3H), 2.96 and 2.87 (ddd, 1H), 2.22-2.07 (m, 2H), 1.95-1.52 (m, 6H),1.42-1.08 (m, 6H) ppm I-181 ¹HNMR (CD₃CN) δ = 7.25-7.03 (m, 6H), 6.58and 5.71 (dd, 1H), 6.46 and 6.39 (d, 1H), 5.35-5.23 (m, 2H), 4.98 and4.67 (m, 1H), 4.42 and 4.34 (d, 1H), 3.84 and 3.63 (m, 1H), 3.34-3.23(m, 2H), 2.96-2.65 (m, 3H), 2.20-2.04 (m, 2H), 2.00-1.58 (m, 6H) ppmI-182 ¹HNMR δ = 7.65-7.57 (m, 2H), 7.33-6.70 (m, 8H), 5.43-5.33 (m, 2H),4.38 and 4.17 (bd, 1H), 3.99 and 3.84 (bd, 1H), 3.43-3.18 (m, 2H), 2.85(t, 1H), 2.38 and 2.20 (s, 3H), 2.17-1.90 (m, 2H), 1.88-1.42 (m, 2H) ppmI-183 ¹HNMR δ = 7.86 (ddd, 1H), 7.68-7.62 (m, 2H), 7.55 (dd, 1H),7.45-7.38 (m, 1H), 7.27 (d, 1H), 7.23 (dd, 1H), 7.18 (t, 1H), 7.03 (t,1H), 6.90 (s, 1H), 5.50-5.32 (m, 2H), 4.38 and 4.12 (d, 1H), 3.99 and3.80 (d, 1H), 3.45-3.15 (m, 2H), 2.86 (dd, 1H), 2.18-2.08 (m, 2H), 1.95and 1.83 (tdd, 1H), 1.59 and 1.43 (tdd, 1H) ppm I-188 ¹HNMR δ = 7.37 and7.30 (s, 1H), 7.18 and 7.16 (t, 1H), 7.03 and 7.02 (t, 1H), 6.90 (s,1H), 6.44 and 5.49 (dd, 1H), 6.35 and 6.24 (d, 1H), 5.45-5.30 (m, 2H),4.35 and 4.28 (d, 1H), 3.94 (d, 1H), 3.40-3.15 (m, 3H), 2.93 and 2.82(dd, 1H), 2.20-2.02 (m, 2H), 1.85-1.48 (m, 6H), 1.37-1.05 (m, 6H) ppmI-189 ¹HNMR δ = 7.52 and 7.38 (s, 1H), 7.17 and 7.15 (t, 1H), 7.13-7.03(m, 4H), 7.03 and 7.02 (t, 1H), 6.90 (s, 1H), 6.54 and 5.67 (dd, 1H),6.45 and 6.38 (d, 1H), 5.45-5.32 (m, 2H), 4.95 and 3.63 (dd, 1H), 4.33and 4.28 (d, 1H), 3.96-3.90 (m, 1H), 3.40-3.20 (m, 2H), 2.85 and 2.80(dd, 1H), 2.82-2.70 (m, 2H), 2.16-1.68 (m, 6H), 1.60-1.49 (m, 2H) ppmI-206 ¹HNMR (CD₃CN) δ = 7.62 (s, 1H), 7.50 (d, 1H), 7.33-7.26 (m, 2H),7.25-7.17 (m, 1H), 6.39 (s, 1H), 5.10 (d, 1H), 5.03 (d, 1H), 4.48 (d,1H), 3.92 (d, 1H), 3.36-3.21 (m, 2H), td (2.84, 1H), 2.48 (s, 3H), 2.22(s, 3H), 2.20-2.09 (m, 2H), 1.85 (tdd, 1H), 1.68 (tdd, 1H) I-207 ¹HNMR δ= 8.05 (s, 1H), 7.76 (dd, 1H), 7.68 (dd, 1H), 7.46 (td, 1H), 7.38 (td,1H), 6.49 (s, 1H), 5.32 (d, 1H), 5.23 (d, 1H), 4.37 (d, 1H), 3.98 (d,1H), 3.43-3.20 (m, 2H), 2.84 (t, 1H), 2.20 (s, 3H), 2.09 (t, 2H), 1.82(tdd, 1H), 1.58 (tdd, 1H) I-208 ¹HNMR δ = 8.14 (s, 1H), 7.62-7.51 (m,1H), 7.28 (d, 1H), 7.26 (d, 1H), 6.49 (s, 1H), 5.32 (d, 1H), 5.23 (d,1H), 4.37 (d, 1H), 3.97 (d, 1H), 3.44-3.20 (m, 2H), 2.85 (t, 1H), 2.21(s, 3H), 2.12 (t, 2H), 1.89-1.76 (m, 1H), 1.65-1.50 (m, 1H) I-210 ¹HNMRδ = 8.44 (d, 1H), 8.12 (s, 1H), 7.75 (d, 1H), 7.35 (dd, 1H), 6.49 (s,1H), 5.32 (d, 1H), 5.23 (d, 1H), 4.37 (d, 1H), 3.98 (d, 1H), 3.44-3.21(m, 2H), 2.85 (t, 1H), 2.46 (s, 3H), 2.21 (s, 3H), 2.08-1.96 (m, 2H),1.88-1.65 (m, 1H), 1.65-1.51 (m, 1H) I-212 ¹HNMR δ = 7.98 (s, 1H), 7.58(s, 1H), 7.51 (d, 1H), 7.33 (m, 2H), 7.24 (m, 1H), 5.60 (d, 1H), 5.50(d, 1H), 4.34 (m, 1H), 3.96 (m, 1H), 3.40-3.25 (m, 2H), 2.86 (m, 1H),2.45 (s, 3H), 2.09 (m, 2H), 1.80 (m, 1H), 1.55 (m, 1H) ppm I-213 ¹HNMR δ= 8.05 (s, 1H), 7.76 (dd, 1H), 7.68 (dd, 1H), 7.58 (s, 1H), 7.45 (td,1H), 7.36 (td, 1H), 5.60 (d, 1H), 5.50 (d, 1H), 4.34 (m, 1H), 3.95 (m,1H), 3.25-3.39 (m, 2H), 2.86 (m, 1H), 2.10 (m, 2H), 1.80 (m, 1H), 1.55(m, 1H) ppm I-214 ¹HNMR δ = 8.14 (s, 1H), 7.60-7.52 (m, 2H), 7.31-7.25(m, 2H), 5.59 (d, 1H), 5.50 (d, 1H), 4.33 (m, 1H), 3.96 (m, 1H),3.49-3.15 (m, 2H), 2.86 (m, 1H), 2.11 (m, 2H), 1.80 (m, 1H), 1.54 (m,1H) ppm I-216 ¹HNMR δ = 8.44 (dd, 1H), 8.12 (s, 1H), 7.75 (d, 1H), 7.58(s, 1H), 7.34 (dd, 1H), 5.60 (d, 1H), 5.50 (d, 1H), 4.34 (m, 1H), 3.97(m, 1H), 3.42-3.26 (m, 2H), 2.87 (m, 1H), 2.46 (s, 3H), 2.12 (m, 2H),1.81 (m, 1H), 1.56 (m, 1H) ppm I-218 ¹HNMR δ = 7.98 (s, 1H), 7.60-7.50(m, 1H), 7.36-7.30 (m, 2H), 7.30-7.21 (m, 1H), 7.18 (t, 1H), 7.02 (t,1H), 6.90 (s, 1H), 5.43 (d, 2H), 4.41-4.32 (m, 1H), 4.02-3.91 (m, 1H),2.90-2.80 (m, 1H), 2.46 (s, 3H), 2.19-2.05 (m, 2H), 1.90-1.73 (m, 1H),1.65-1.52 (m, 1H) I-219 ¹HNMR δ = 8.05 (s, 1H), 7.76 (d, 1H), 7.69 (d,1H), 7.46 (t, 1H), 7.39 (t, 1H), 7.18 (t, 1H), 7.02 (t, 1H), 6.90 (s,1H), 5.39 (d, 2H), 4.40-4.29 (m, 1H), 4.01-3.91 (m, 1H), 2.92-2.81 (m,1H), 2.19-2.06 (m, 2H), 1.89-1.74 (m, 1H), 1.65-1.50 (m, 1H) I-220 ¹HNMRδ = 8.14 (s, 1H), 7.65-7.52 (m, 1H), 7.30-7.21 (m, 2H), 7.18 (t, 1H),7.02 (t, 1H), 6.90 (s, 1H), 5.39 (d, 2H), 4.40-4.29 (m, 1H), 4.02-3.91(m, 1H), 2.90-2.77 (m, 1H), 2.18-2.02 (m, 2H), 1.90-1.76 (m, 1H),1.68-1.51 (m, 1H) I-222 ¹HNMR δ = 8.45 (bs, 1H), 8.12 (s, 1H), 7.75 (d,1H), 7.38-7.33 (m, 1H), 7.18 (t, 1H), 7.02 (t, 1H), 6.90 (s, 1H), 5.39(d, 2H), 4.39-4.31 (m, 1H), 4.01-3.92 (m, 1H), 3.00-2.78 (m, 1H), 2.46(s, 3H), 2.18-2.03 (m, 2H), 1.89-1.76 (m, 1H), 1.65-1.52 (m, 1H) I-223¹HNMR δ = 8.02 (s, 1H), 7.15 (t, 1H), 7.02 (t, 1H), 6.90 (s, 1H), 5.38(d, 2H), 4.39-4.30 (m, 1H), 4.04-3.91 (m, 1H), 2.87-2.79 (m, 1H), 2.28(s, 3H), 2.16-2.04 (m, 2H), 1.90-1.73 (m, 1H), 1.62-1.49 (m, 1H) I-224¹HNMR δ = 7.98 (s, 1H), 7.50 (d, 1H), 7.47-7.42 (m, 2H), 7.39-7.32 (m,3H), 7.27-7.20 (m, 1H), 4.46-4.38 (m, 1H), 4.12-4.04 (m, 1H), 3.88 (d,2H), 2.85-2.76 (m, 1H), 2.46 (s, 3H), 2.17-2.05 (m, 2H), 1.79-1.67 (m,1H), 1.62-1.48 (m, 1H) I-225 ¹HNMR δ = 8.05 (s, 1H), 7.76 (d, 1H), 7.68(d, 1H), 7.50-7.44 (m, 3H), 7.41-7.30 (m, 2H), 4.46-4.36 (m, 1H),4.11-4.02 (m, 1H), 3.87 (d, 2H), 2.86-2.74 (m, 1H), 2.17-2.05 (m, 2H),1.80-1.68 (m, 1H), 1.64-1.50 (m, 1H) I-226 ¹HNMR δ = 8.13 (s, 1H),7.65-7.52 (m, 2H), 7.49-7.43 (m, 2H), 7.35 (d, 1H), 7.25 (t, 1H),4.46-4.37 (m, 1H), 4.13-4.04 (m, 1H), 3.88 (d, 2H), 2.86-2.75 (m, 1H),2.18-2.04 (m, 2H), 1.80-1.69 (m, 1H), 1.62-1.50 (m, 1H) I-228 ¹HNMR δ =8.46 (bs, 1H), 8.12 (s, 1H), 7.76 (d, 1H), 7.68-7.52 (m, 1H), 7.48-7.42(m, 2H), 7.39-7.32 (m, 1H), 4.46-4.39 (m, 1H), 4.13-4.04 (m, 1H), 3.87(d, 2H), 2.88-2.75 (m, 1H), 2.47 (s, 3H), 2.18-2.05 (m, 2H), 1.81-1.69(m, 1H), 1.62-1.50 (m, 1H) I-229 ¹HNMR δ = 8.01 (s, 1H), 7.47-7.41 (m,2H), 7.34 (d, 1H), 4.44-4.35 (m, 1H), 4.12-4.04 (m, 1H), 3.87 (d, 2H),2.86-2.75 (m, 1H), 2.28 (s, 3H), 2.17-2.04 (m, 2H), 1.80-1.68 (m, 1H),1.61-1.50 (m, 1H) I-230 ¹HNMR δ = 7.97 (s, 1H), 7.51 (d, 1H), 7.34 (d,2H), 7.28-7.20 (m, 1H), 7.03 (d, 1H), 6.93 (d, 1H), 6.90 (s, 1H), 4.48(d, 1H), 3.97 (d, 1H), 3.69 (d, 1H), 3.64 (d, 1H), 3.40-3.25 (m, 1H),3.20 (t, 1H), 2.78 (t, 1H), 2.45 (s, 3H), 2.24 (s, 3H), 2.15 (s, 3H),2.02 (t, 2H), 1.65-1.47 (m, 2H) I-231 ¹HNMR δ = 8.03 (s, 1H), 7.76 (dd,1H), 7.68 (dd, 1H), 7.45 (td, 1H), 7.38 (td, 1H), 7.03 (d, 1H), 6.93 (d,1H), 6.88 (s, 1H), 4.48 (d, 1H), 3.98 (d, 1H), 3.70 (d, 1H), 3.64 (d,1H), 3.40-3.26 (m, 1H), 3.20 (t, 1H), 2.79 (t, 1H), 2.23 (s, 3H), 2.15(s, 3H), 2.03 (t, 2H), 1.68-1.47 (m, 2H) I-232 ¹HNMR δ = 8.12 (s, 1H),7.62-7.51 (m, 1H), 7.27 (t, 2H), 7.03 (d, 1H), 6.93 (d, 1H), 6.90 (s,1H), 4.53-4.45 (m, 1H), 4.01-3.93 (m, 1H), 3.69 (d, 1H), 3.63 (d, 1H),3.40-3.15 ‘m, 2H), 2.78 (t, 1H), 2.23 (s, 3H), 2.15 (s, 3H), 2.14-2.00(m, 2H), 1.68-1.48 (m, 2H) I-235 ¹HNMR δ = 8.00 (s, 1H), 7.03 (d, 1H),6.93 (d, 1H), 6.89 (s, 1H), 4.48 (d, 1H), 3.96 (d, 1H), 3.68 (d, 1H),3.63 (d, 1H), 3.40-3.15 (m, 2H), 2.77 (t, 1H), 2.28 (s, 3H), 2.23 (s,3H), 2.15 (s, 3H), 2.04 (t, 2H), 1.65-1.48 (m, 2H) I-236 ¹HNMR δ = 8.40(dd, 1H), 7.74-7.56 (m, 5H), 7.17 (dd, 1H), 5.62 (d, 1H), 5.50 (d, 1H),4.37 (m, 1H), 3.97 (m, 1H), 3.50-3.20 (m, 2H), 2.87 (m, 1H), 2.40 (s,3H), 2.12 (m, 2H), 1.85 (m, 1H), 1.57 (m, 1H) ppm I-237 ¹HNMR δ =7.68-7.50 (m, 3H), 7.25-7.15 (m, 3H), 7.11 (d, 1H), 7.03 (d, 1H), 6.93(d, 1H), 6.90 (s, 1H), 4.51 (d, 1H), 3.97 (d, 1H), 3.71 (d, 1H), 3.63(d, 1H), 3.40-3.15 (m, 2H), 2.79 (t, 1H), 2.38 (s, 3H), 2.24 (s, 3H),2.14 (s, 3H), 2.12-2.00 (m, 2H), 1.65-1.48 (m, 2H) I-238 ¹HNMR δ = 7.92(s, 1H), 7.02 (d, 1H), 6.93 (d, 1H), 6.89 (s, 1H), 4.46 (d, 1H), 4.22(s, 1H), 3.95 (d, 1H), 3.68 (d, 1H), 3.62 (d, 1H), 3.34-3.23 (m, 1H),3.18 (t, 1H), 2.77 (t, 1H), 2.23 (s, 3H), 2.14 (s, 3H), 2.02 (t, 2H),1.63-1.44 (m, 2H) I-239 ¹HNMR δ = 7.93 (s, 1H), 7.17 (t, 1H), 7.02 (t,1H), 6.90 (s, 1H), 5.38 (d, 2H), 4.37-4.30 (m, 1H), 4.23 (s, 1H),4.01-3.89 (m, 1H), 2.89-2.77 (m, 1H), 2.15-2.00 (m, 2H), 1.84-1.70 (m,1H), 1.61-1.49 (m, 1H) I-240 ¹HNMR δ = 7.73 (s, 1H), 7.59 (s, 1H), 7.54(d, 1H), 7.42-7.27 (m, 4H), 5.63 (d, 1H), 5.50 (d, 1H), 4.37 (d, 1H),3.98 (d, 1H), 3.45-3.20 (m, 2H), 2.87 (dd, 1H), 2.18-2.08 (m, 2H), 1.83(tdd, 1H), 1.58 (tdd, 1H) ppm I-241 ¹HNMR δ = 7.73 (s, 1H), 7.54 (d,1H), 7.42-7.27 (m, 4H), 7.19 (t, 1H), 7.03 (t, 1H), 6.91 (s, 1H), 5.45(d, 1H), 5.36 (d, 1H), 4.38 (d, 1H), 4.01 (d, 1H), 3.45-3.22 (m, 2H),2.86 (dd, 1H), 2.20-2.09 (m, 2H), 1.83 (tdd, 1H), 1.60 (tdd, 1H) ppmI-242 ¹HNMR δ = 7.92 (d, 1H), 7.73 (s, 1H), 7.58-7.53 (dd, 1H),7.45-7.28 (m, 3H), 6.50 (s, 1H), 5.34 (d, 1H), 5.23 (d, 1H), 4.40 (d,1H), 3.99 (d, 1H), 3.43-3.20 (m, 2H), 2.85 (dd, 1H), 2.21 (s, 3H),2.18-2.09 (m, 2H), 1.84 (tdd, 1H), 1.59 (tdd, 1H) ppm

The chemical NMR shifts were measured in ppm at 400 MHz, unlessindicated otherwise in the solvent DMSO-d₆ using tetramethylsilane asinternal standard.

The following abbreviations describe signal splitting:

b=broad, s=singlet, d=doublet, t=triplet, q=quadruplet, m=multiplet

USE EXAMPLES Example A Phytophthora Test (Tomato)/Protective

Solvent: 49 parts by weight of N,N-dimethylformamide Emulsifier:  1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young tomato plants are sprayed withthe preparation of active compound at the stated application rate. 1 dayafter the treatment, the plants are inoculated with a spore suspensionof Phytophthora infestans and then remain at 100% rel. humidity and 22°C. for 24 h. The plants are then placed in a climatized chamber at about96% relative atmospheric humidity and a temperature of about 20° C.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the compounds according to the invention I-1, I-2, I-3,I-9, I-15, I-26, I-27, I-35, I-43, I-50, I-51, I-52, I-53, I-59, I-74,I-77, I-79, I-80, I-81, I-83, I-93, I-96, I-98, I-99, I-100, I-101,I-102, I-103, I-104, I-105, I-107, I-108, I-109, I-114, I-115, I-116,I-117, I-121, I-122 and I-123 show, at an active compound concentrationof 500 ppm, an efficacy of 70% or more.

Example B Plasmopara Test (Grapevine)/Protective

Solvents: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier:   1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvents andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Plasmopara viticola and then remain in an incubationcabin at about 20° C. and 100% relative atmospheric humidity for 1 day.The plants are then placed in a greenhouse at about 21° C. and anatmospheric humidity of about 90% for 4 days. The plants are thenmoistened and placed in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the compounds according to the invention I-1, I-9, I-35,I-43, I-50, I-51, I-53, I-59, I-74, I-80, I-81, I-93, I-96, I-98, I-99,I-100, I-101, I-102, I-103, I-104, I-105, I-108, I-109, I-114, I-115,I-116 and I-117 show, at an active compound concentration of 100 ppm, anefficacy of 70% or more.

1. Compounds of the formula (I),

in which the symbols have the following meanings: A represents methyl orA represents unsubstituted or substituted phenyl, where the substituentsindependently of one another are selected from the list below cyano,nitro, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,C₃-C₆-halocycloalkyl, C₄-C₁₀-cycloalkylalkyl, C₄-C₁₀-alkylcycloalkyl,C₅-C₁₀-alkylcycloalkylalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, benzyl, phenyl,hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, OCH₂OCH₃, SH, C₁-C₄-alkylthio,C₁-C₆-haloalkylthio, CHO, COOH, (C₁-C₄-alkoxy)carbonyl, CONR⁶R⁷,CR⁶═NOR⁷, (C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,(C₁-C₄-alkyl)carbonyloxy, (C₁-C₄-alkyl)carbonylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylsulphonyl, NR⁶R⁷, NR⁶COR⁷, SF₅, SO₂NR⁶R⁷,C₂-C₄-alkoxyalkyl or 1-methoxycyclopropyl or A is an optionallybenzo-fused unsubstituted or substituted 5- or 6-membered heteroaryl,where the substituents independently of one another are selected fromthe list below Substituents at Carbon: cyano, nitro, halogen,C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkylC₄-C₁₀-cycloalkylalkyl, C₄-C₁₀-alkylcycloalkyl,C₅-C₁₀-alkylcycloalkylalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, benzyl, phenyl,hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, OCH₂OCH₃, SH, C₁-C₄-alkylthio,C₁-C₆-haloalkylthio, CHO, COOH, (C₁-C₄-alkoxy)carbonyl, CONR⁶R⁷,CR⁶═NOR⁷, (C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,(C₁-C₄-alkyl)carbonyloxy, (C₁-C₄-alkyl)carbonylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylsulphonyl, NR⁶R⁷, NR⁶COR⁷, SF₅, SO₂NR⁶R⁷,C₂-C₄-alkoxyalkyl or 1-methoxycyclopropyl Substituents at Nitrogen:hydroxyl, NR⁶R⁷, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl, C₂-C₆-alkenyl,C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, or C₂-C₆-haloalkynyl L¹ represents(C(R¹)₂)_(n) where n=0 to 3 R¹ are identical or different andindependently of one another represent hydrogen, halogen, C₁-C₂-alkyl,C₁-C₂-haloalkyl or cyano, with the provision that L¹ may contain at mosttwo R¹ different from hydrogen Y represents sulphur or oxygen, Wrepresents an unsubstituted or monosubstituted C₁- to C₃-carbon chain,where the substituent is selected from the group consisting of oxo,hydroxyl, cyano and C₁-C₄-alkyl X represents an unsubstituted ormonosubstituted C₁- to C₂-carbon chain, where the substituent isselected from the group consisting of oxo, hydroxyl, cyano andC₁-C₄-alkyl R² represents hydrogen, C₁-C₂-alkyl, C₁-C₂-haloalkyl orhalogen L² represents —C(R⁸)₂—C(R⁸)₂— or —CR⁹═CR⁹— or —C≡C— L³represents a direct bond or L³ represents a C₁- to C₄-carbon chain whichmay contain up to two substituents, where the substituents independentlyof one another are selected from the list below: halogen, C₁-C₂-alkyl,C₁-C₂-alkoxy, C₁-C₂-haloalkyl or C₃-C₆-cycloalkyl R³ represents methyl,C₁-C₂-haloalkyl, —CH═CH₂, —C≡CH, or unsubstituted or monosubstitutedC₃-C₁₀-cycloalkyl, where the substituent is selected from the listbelow: cyano, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl,tri(C₁-C₂-alkyl)silyl, phenyl, hydroxyl, oxo, C₁-C₆-alkoxy,C₁-C₆-haloalkoxy, C₂-C₆-alkenyloxy, C₂-C₆-alkynyloxy, C₁-C₆-alkylthio orC₁-C₆-haloalkylthio, or R³ represents unsubstituted or substitutedphenyl, where the substituents independently of one another are selectedfrom the list below: cyano, nitro, halogen, C₁-C₆-alkyl,C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,C₄-C₁₀-cycloalkylalkyl, C₄-C₁₀-halocycloalkylalkyl,C₄-C₁₀-alkylcycloalkyl, C₅-C₁₀-alkylcycloalkylalkyl,C₄-C₁₀-cycloalkoxyalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,C₃-C₈-cycloalkenyl, C₃-C₈-halocycloalkenyl, C₂-C₆-alkynyl,C₂-C₆-haloalkynyl, C₂-C₆-alkoxyalkyl, C₂-C₆-haloalkoxyalkyl,C₃-C₈-alkoxyalkoxyalkyl, tri(C₁-C₂-alkyl)silyl, benzyl, phenyl,hydroxyl, C₁-C₆-alkoxy, C₂-C₆-alkoxyalkoxy, C₁-C₆-haloalkoxy,C₂-C₆-alkenyloxy, C₂-C₆-haloalkenyloxy, C₂-C₆-alkynyloxy,C₂-C₆-haloalkynyloxy, C₃-C₆-cycloalkoxy, C₃-C₆-cycloalkyloxy,C₃-C₆-halocycloalkoxy, C₄-C₁₀-cycloalkylalkyloxy, NR⁶R⁷, SH, SF₅,C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₂-C₆-alkylalkylthio,C₃-C₆-cycloalkylthio, CHO, COOH, (C₁-C₆-alkoxy)carbonyl, CONR⁶R⁷,CR⁶═NOR⁷, (C₁-C₆-alkyl)carbonyl, (C₁-C₆-haloalkyl)carbonyl,(C₁-C₆-alkyl)carbonyloxy, (C₁-C₆-haloalkyl)carbonyloxy,(C₁-C₆-alkyl)carbonylthio, C₁-C₆-alkylsulphinyl,C₁-C₆-haloalkylsulphinyl, C₁-C₆-alkylsulphonyl,C₁-C₆-haloalkylsulphonyl, NR⁶COR⁷ or SO₂NR⁶R⁷ or R³ represents saturatedor partially or fully unsaturated naphthyl or indenyl, which may containup to two substituents, where the substituents independently of oneanother are selected from the list below: cyano, halogen, C₁-C₆-alkyl,C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, phenyl,hydroxyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyloxy,C₂-C₆-alkynyloxy, C₁-C₆-alkylthio or C₁-C₆-haloalkylthio, or R³represents an unsubstituted or substituted 5- or 6-membered heteroarylradical, where the substituents independently of one another areselected from the list below: substituents at carbon: cyano, nitro,halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,C₃-C₆-halocycloalkyl C₄-C₁₀-cycloalkylalkyl, C₄-C₁₀-alkylcycloalkyl,C₅-C₁₀-alkylcycloalkylalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, benzyl, phenyl,hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, OCH₂OCH₃, SH, C₁-C₄-alkylthio,C₁-C₆-haloalkylthio, COOH, (C₁-C₄-alkoxy)carbonyl, CONR⁶R⁷,(C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,(C₁-C₄-alkyl)carbonyloxy, (C₁-C₄-alkyl)carbonylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylsulphonyl, NR⁶R⁷, NR⁶COR⁷, SF₅, SO₂NR⁶R⁷,C₂-C₄-alkoxyalkyl or 1-methoxycyclopropyl substituents at nitrogen:hydroxyl, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl, C₂-C₆-alkenyl,C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl or phenyl or R³represents benzo-fused unsubstituted or substituted 5- or 6-memberedheteroaryl which may contain up to two substituents, where thesubstituents independently of one another are selected from the listbelow: substituents at carbon: cyano, nitro, halogen, C₁-C₆-alkyl,C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkylC₄-C₁₀-cycloalkylalkyl, C₄-C₁₀-alkylcycloalkyl,C₅-C₁₀-alkylcycloalkylalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl, benzyl, phenyl,hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, OCH₂OCH₃, SH, C₁-C₄-alkylthio,C₁-C₆-haloalkylthio, COOH, (C₁-C₄-alkoxy)carbonyl, CONR⁶R⁷,(C₁-C₄-alkyl)carbonyl, (C₁-C₄-haloalkyl)carbonyl,(C₁-C₄-alkyl)carbonyloxy, (C₁-C₄-alkyl)carbonylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylsulphonyl, NR⁶R⁷, NR⁶COR⁷, SF₅, SO₂NR⁶R⁷,C₂-C₄-alkoxyalkyl or 1-methoxycyclopropyl substituents at nitrogen:C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,C₄-C₁₀-alkylcycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl,C₂-C₆-haloalkynyl or phenyl or R³ is an unsubstituted or monosubstituted5- to 15-membered heterocyclyl radical which is attached via a carbonatom and which may contain up to two further heteroatoms selected fromthe group consisting of nitrogen, oxygen and sulphur, where thesubstituent is selected from the list below: substituents at carbon:cyano, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl,C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl,tri(C₁-C₂-alkyl)silyl, phenyl, hydroxyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₂-C₆-alkenyloxy, C₂-C₆-alkynyloxy, C₁-C₆-alkylthio orC₁-C₆-haloalkylthio substituents at nitrogen: C₁-C₆-alkyl,C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, tri(C₁-C₂-alkyl)silyl or phenyl R⁶, R⁷independently of one another represent hydrogen, C₁-C₄-alkyl,C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, R⁸ are identical or different andindependently of one another represent hydrogen, halogen, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₃-C₆-cycloalkyl or C₁-C₃-haloalkyl, R⁹ are identical ordifferent and independently of one another represent hydrogen,C₁-C₄-alkyl or C₃-C₆-cycloalkyl, and also the agrochemically activesalts thereof.
 2. Compounds of the formula (I) according to claim 1 inwhich the symbols have the following meanings: A represents methyl or Arepresents phenyl which may contain up to two substituents, where thesubstituents independently of one another are selected from the listbelow: cyano, nitro, halogen, C₁-C₄-alkyl, C₁-C₃-haloalkyl,C₃-C₆-cycloalkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, hydroxyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio,(C₁-C₄-alkoxy)carbonyl, (C₁-C₄-alkyl)carbonyl,(C₁-C₄-haloalkyl)carbonyl, C₁-C₄-alkylsulphinyl,C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl orC₁-C₄-haloalkylsulphonyl, or A represents a heteroaromatic radicalselected from the group below: furan-2-yl, furan-3-yl, thiophen-2-yl,thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl,1H-pyrrol-1-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, oxazol-2-yl,oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl,1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl,1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl,1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl,1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl, pyridin-2-yl, pyridin-3-yl,pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl,pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, 1,3,5-triazin-2-yl,1,2,4-triazin-3-yl, 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl,1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl,1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl,benzimidazol-5-yl, 1H-indazol-1-yl, 1H-indazol-3-yl, 1H-indazol-4-yl,1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl, 2H-indazol-2-yl,1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl,1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl,1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl,1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl,1,3-benzothiazol-2-yl, 1,3-benzoxazol-2-yl, quinolin-2-yl,quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl,quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl,isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-ylor isoquinolin-8-yl, which may contain up to two substituents, where thesubstituents independently of one another are selected from the listbelow: substituents at carbon: cyano, halogen, C₁-C₄-alkyl,C₁-C₃-haloalkyl, hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio or C₁-C₄-haloalkylthio, substituents at nitrogen:C₁-C₄-alkyl, C₁-C₃-haloalkyl, cyclopropyl, C₂-C₄-alkenyl orC₂-C₄-alkynyl, L¹ represents (C(R¹)₂)_(n) where n=0 to 3 R¹ areidentical or different and independently of one another representhydrogen, chlorine, fluorine, methyl, CF₃ or cyano, with the provisionthat L¹ may contain at most two R¹ different from hydrogen, Y representssulphur or oxygen, W represents an unsubstituted or monosubstituted C₁-to C₂-carbon chain, where the substituent is selected from the groupconsisting of cyano and C₁-C₂-alkyl X represents an unsubstituted ormonosubstituted C₁- to C₂-carbon chain, where the substituent isselected from the group consisting of cyano and C₁-C₂-alkyl, R²represents hydrogen, C₁-C₂-alkyl or halogen, L² represents—C(R⁸)₂—C(R⁸)₂— or —CR⁹═CR⁹— or —C≡C—, L³ represents a direct bond, orL³ represents a C₁- to C₄-carbon chain which may contain up to twosubstituents, where the substituents independently of one another areselected from the list below: C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-haloalkylor cyclopropyl, R³ represents methyl, C₁-C₂-haloalkyl, —CH═CH₂, —C≡CH,or unsubstituted or monosubstituted C₃-C₁₀-cycloalkyl, where thesubstituent is selected from the list below: halogen, C₁-C₆-alkyl,C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, tri(C₁-C₂-alkyl)silyl,phenyl or oxo, or R³ represents phenyl which may contain up to threesubstituents, where the substituents independently of one another areselected from the list below: cyano, nitro, halogen, C₁-C₆-alkyl,C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₂-C₆-alkenyl,C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl,tri(C₁-C₂-alkyl)silyl, phenyl, hydroxyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkylthio or C₁-C₆-haloalkylthio, or R³ representsnaphthalen-1-yl, naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,1,2,3,4-tetrahydronaphthalen-2-yl, 5,6,7,8-tetrahydronaphthalen-1-yl,5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl, 2,3-dihydro-1H-inden-1-yl,2,3-dihydro-1H-inden-2-yl, 2,3-dihydro-1H-inden-4-yl or2,3-dihydro-1H-inden-5-yl, which may contain up to two substituents,where the substituents independently of one another are selected fromthe list below: cyano, halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl,C₃-C₆-cycloalkyl, phenyl, hydroxyl, C₁-C₆-alkoxy, C₁-C₃-haloalkoxy,C₁-C₆-alkylthio or C₁-C₃-haloalkylthio, or R³ represents furan-2-yl,furan-3-yl, thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl,isoxazol-5-yl, 1H-pyrrol-1-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl,oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl,thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl,pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,imidazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl,1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl, 1,2,4-tri-azol-3-yl,pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl,pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl,pyrazin-2-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, which may containup to two substituents, where the substituents independently of oneanother are selected from the list below: substituents at carbon: cyano,halogen, C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, phenyl,hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio orC₁-C₄-haloalkylthio, substituents at nitrogen: C₁-C₆-alkyl,C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl orphenyl, or R³ represents 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl,1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl,1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl,benzimidazol-5-yl, 1H-indazol-1-yl, 1H-indazol-3-yl, 1H-indazol-4-yl,1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl, 2H-indazol-2-yl,1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl,1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl,1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl,1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl,quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl,quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl,isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl,isoquinolin-7-yl or isoquinolin-8-yl, which may contain up to twosubstituents, where the substituents independently of one another areselected from the list below: substituents at carbon: cyano, halogen,C₁-C₆-alkyl, C₁-C₃-haloalkyl, C₃-C₆-cycloalkyl, phenyl, hydroxyl,C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio,substituents at nitrogen: C₁-C₆-alkyl, C₁-C₃-haloalkyl,C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or phenyl, or R³represents an unsubstituted or monosubstituted 5- to 6-memberedheterocyclyl radical which is attached via a carbon atom and which maycontain up to two further heteroatoms selected from the group consistingof nitrogen, oxygen and sulphur, where the substituent is selected fromthe list below: substituents at carbon: C₁-C₆-alkyl, C₁-C₃-haloalkyl,C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, tri(C₁-C₂-alkyl)silyl orphenyl, substituents at nitrogen: C₁-C₆-alkyl, C₃-C₆-cycloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, tri(C₁-C₂-alkyl)silyl or phenyl, R⁸ areidentical or different and independently of one another representhydrogen, halogen, C₁-C₂-alkyl, C₁-C₂-alkoxy, cyclopropyl orC₁-C₂-haloalkyl, R⁹ are identical or different and independently of oneanother represent hydrogen, C₁-C₂-alkyl or cyclopropyl and also theagrochemically active salts thereof.
 3. Compounds of the formula (I)according to one or more of claims 1 to 2 in which the symbols have thefollowing meanings, A represents methyl, or A represents phenyl whichmay contain up to two substituents, where the substituents independentlyof one another are selected from the list below: cyano, nitro, halogen,C₁-C₂-alkyl, C₁-C₂-haloalkyl, hydroxyl, C₁-C₂-alkoxy orC₁-C₂-haloalkoxy, or A represents a heteroaromatic radical selected fromthe group below: furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl,oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl,thiazol-5-yl; pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl,imidazol-2-yl, imidazol-4-yl, 1,2,4-triazol-1-yl, pyridin-2-yl,pyridin-3-yl, pyridin-4-yl, 1,2,4-triazin-3-yl, 1H-benzimidazol-2-yl or1,3-benzothiazol-2-yl, which may contain up to two substituents, wherethe substituents independently of one another are selected from the listbelow: substituents at carbon: cyano, halogen, C₁-C₂-alkyl,C₁-C₂-haloalkyl, hydroxyl, C₁-C₂-alkoxy or C₁-C₂-haloalkoxy,substituents at nitrogen: C₁-C₂-alkyl or C₁-C₂-haloalkyl, L¹ represents(C(R¹)₂)_(n) where n=0 to 3, R¹ are identical or different andindependently of one another represent hydrogen or methyl, with theprovision that L¹ may contain at most two methyl substituents, Yrepresents sulphur or oxygen, W represents —CH₂CH₂—, X represents—CH₂CH₂—, R² represents hydrogen, methyl or halogen, L² represents—C(R⁸)₂—C(R⁸)₂— or —CR⁹═CR⁹— or —C≡C—, L³ represents a direct bond, orL³ represents a C₁- to C₄-carbon chain which may contain up to twosubstituents, where the substituents independently of one another areselected from the list below: methyl, methoxy or CF₃, R³ representsmethyl, C₁-C₂-haloalkyl, —CH═CH₂, —C≡CH, or unsubstituted ormonosubstituted C₃-C₁₀-cycloalkyl, where the substituent is selectedfrom the list below: fluorine, chlorine, methyl, ethyl, cyclopropyl,cyclopentyl or cyclohexyl, or R³ represents phenyl which may contain upto three substituents, where the substituents independently of oneanother are selected from the list below: cyano, halogen, C₁-C₆-alkyl,C₁-C₃-haloalkyl, phenyl, hydroxyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkylthio or C₁-C₆-haloalkylthio, or R³ representsnaphthalen-1-yl, naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,1,2,3,4-tetrahydronaphthalen-2-yl, 5,6,7,8-tetrahydronaphthalen-1-yl,5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl, 2,3-dihydro-1H-inden-1-yl,2,3-dihydro-1H-inden-2-yl, 2,3-dihydro-1H-inden-4-yl or2,3-dihydro-1H-inden-5-yl, which may contain up to two substituents,where the substituents independently of one another are selected fromthe list below: fluorine, chlorine, bromine, iodine, methyl, ethyl, CF₃,CHF₂, cyclopropyl, phenyl, hydroxyl, OMe, OEt, OCF₃, OCHF₂, OC₂F₅, SMeor SCF₃, or R³ represents furan-2-yl, furan-3-yl, thiophen-2-yl,thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl,1H-pyrrol-1-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, oxazol-2-yl,oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl,1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl,1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl,1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl,1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl, pyridin-2-yl, pyridin-3-yl,pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl,pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, 1,3,5-triazin-2-yl or1,2,4-triazin-3-yl, which may contain up to two substituents, where thesubstituents independently of one another are selected from the listbelow: substituents at carbon: cyano, fluorine, chlorine, bromine,iodine, methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, CF₃, CHF₂,C₂F₅, CCl₃, cyclopropyl, phenyl, hydroxyl, OMe, OEt, OisoPr, OCF₃,OCHF₂, OC₂F₅, SMe or SCF₃, substituents at nitrogen: methyl, ethyl,1-methylethyl, 1,1-dimethylethyl, cyclopropyl or phenyl, or R³represents 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl, 1H-indol-4-yl,1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl, 1H-benzimidazol-1-yl,1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl, benzimidazol-5-yl,1H-indazol-1-yl, 1H-indazol-3-yl, 1H-indazol-4-yl, 1H-indazol-5-yl,1H-indazol-6-yl, 1H-indazol-7-yl, 2H-indazol-2-yl, 1-benzofuran-2-yl,1-benzofuran-3-yl, 1-benzofuran-4-yl, 1-benzofuran-5-yl,1-benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl,1-benzothiophen-3-yl, 1-benzothiophen-4-yl, 1-benzothiophen-5-yl,1-benzothiophen-6-yl, 1-benzothiophen-7-yl, quinolin-2-yl,quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl,quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl,isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-ylor isoquinolin-8-yl, which may contain up to two substituents, where thesubstituents independently of one another are selected from the listbelow: substituents at carbon: cyano, fluorine, chlorine, bromine,iodine, methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, CF₃, CHF₂,C₂F₅, CCl₃, cyclopropyl, phenyl, hydroxyl, OMe, OEt, OisoPr, OCF₃,OCHF₂, OC₂F₅, SMe or SCF₃, substituents at nitrogen: methyl, ethyl,1-methylethyl, 1,1-dimethylethyl, cyclopropyl or phenyl, or R³represents unsubstituted or monosubstituted pyrrolidin-2-yl,pyrrolidin-3-yl, morpholin-3-yl, morpholin-2-yl, piperidin-2-yl,piperidin-3-yl or piperazin-2-yl, where the substituent is selected fromthe list below: substituents at carbon: methyl, ethyl, CF₃, cyclopropylor phenyl, substituents at nitrogen: methyl, ethyl, cyclopropyl orphenyl, R⁸ are identical or different and independently of one anotherrepresent hydrogen, methyl, ethyl or CF₃, R⁹ are identical or differentand independently of one another represent hydrogen, methyl or ethyl,and also the agrochemically active salts thereof.
 4. Compounds of theformula (I) according to one or more of claims 1 to 3 in which thesymbols have the following meanings, A represents methyl, or Arepresents phenyl which may contain up to two substituents, where thesubstituents independently of one another are selected from the listbelow: cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, CF₃,CHF₂, C₂F₅, CCl₃, hydroxyl, OMe, OCF₃, OCHF₂, OCH₂CF₃ or OC₂F₅, or Arepresents a heteroaromatic radical selected from the group below:thiophen-3-yl, pyrazol-1-yl, pyrazol-4-yl, pyridin-4-yl,1H-benzimidazol-2-yl or 1,3-benzothiazol-2-yl, which may contain up totwo substituents, where the substituents independently of one anotherare selected from the list below: substituents at carbon: cyano,fluorine, chlorine, bromine, iodine, methyl, ethyl, CF₃, CHF₂, C₂F₅,CCl₃, hydroxyl, OMe, OCF₃, OCHF₂, OCH₂CF₃ or OC₂F₅, substituents atnitrogen: methyl, ethyl or CF₃, L¹ represents (C(R¹)₂)_(n) where n=0 to3, R¹ are identical or different and independently of one anotherrepresent hydrogen or methyl, with the provision that L¹ may contain atmost one methyl substituent, Y represents sulphur or oxygen, Wrepresents —CH₂CH₂—, X represents —CH₂CH₂—, R² represents hydrogen,methyl, chlorine or bromine, L² represents —C(R⁸)₂—C(R⁸)₂— or —CR⁹═CR⁹—or —C≡C—, L³ represents a direct bond, or L³ represents a C₁- toC₄-carbon chain, R³ represents methyl, CF₃, —CH═CH₂, —C≡CH, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, or R³represents phenyl which may contain up to two substituents, where thesubstituents independently of one another are selected from the listbelow: cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl,1-methylethyl, 1,1-dimethylethyl, CF₃, CHF₂, C₂F₅, CCl₃, phenyl,hydroxyl, OMe, OEt, OisoPr, OCF₃, OCHF₂, OC₂F₅, SMe or SCF₃, or R³represents naphthalen-1-yl, naphthalen-2-yl,1,2,3,4-tetrahydronaphthalen-1-yl, 1,2,3,4-tetrahydronaphthalen-2-yl,5,6,7,8-tetrahydronaphthalen-1-yl, 5,6,7,8-tetrahydronaphthalen-2-yl,decalin-1-yl, decalin-2-yl, 1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl,1H-inden-4-yl, 1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl,2,3-dihydro-1H-inden-1-yl, 2,3-dihydro-1H-inden-2-yl,2,3-dihydro-1H-inden-4-yl or 2,3-dihydro-1H-inden-5-yl, or R³ representsfuran-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl,isoxazol-4-yl, isoxazol-5-yl, 1H-pyrrol-1-yl, 1H-pyrrol-2-yl,1H-pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl,thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl,isothiazol-5-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl,imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, 1,2,4-oxadiazol-3-yl,1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl,1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl,1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl,1,2,4-triazol-3-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl,pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl,pyrimidin-5-yl, pyrazin-2-yl, 1,3,5-triazin-2-yl or 1,2,4-triazin-3-yl,or R³ represents 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl,1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl,1H-benzimidazol-1-yl, 1H-benzimidazol-2-yl, 1H-benzimidazol-4-yl,benzimidazol-5-yl, 1H-indazol-1-yl, 1H-indazol-3-yl, 1H-indazol-4-yl,1H-indazol-5-yl, 1H-indazol-6-yl, 1H-indazol-7-yl, 2H-indazol-2-yl,1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl,1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl,1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl,1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl,quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl,quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl,isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl,isoquinolin-7-yl or isoquinolin-8-yl, or R³ represents pyrrolidin-2-yl,pyrrolidin-3-yl, morpholin-3-yl, morpholin-2-yl, piperidin-2-yl,piperidin-3-yl or piperazin-2-yl, R⁸ are identical or different andindependently of one another represent hydrogen, methyl or ethyl, R⁹ areidentical or different and independently of one another representhydrogen, methyl or ethyl, and also the agrochemically active saltsthereof.
 5. Method for controlling phytopathogenic harmful fungi,characterized in that compounds of the formula (I) according to one ormore of claims 1 to 4 are applied to the phytopathogenic harmful fungiand/or their habitat.
 6. Compositions for controlling phytopathogenicharmful fungi, characterized in that they comprise at least one compoundaccording to one or more of claims 1 to 4, in addition to extendersand/or surfactants.
 7. Use of heterocyclyl-substituted thiazoles of theformula (I) according to one or more of claims 1 to 4 for controllingphytopathogenic harmful fungi.
 8. Process for preparing compositions forcontrolling phytopathogenic harmful fungi, characterized in thatheterocyclyl-substituted thiazoles of the formula (I) according to oneor more of claims 1 to 4 are mixed with extenders and/or surfactants. 9.Process for preparing the compounds of the formula (I), comprising atleast one of steps (a) to (n) below: (a) the conversion of compounds ofthe formula (VII) in the presence of an organometallic compound R⁹-Mand, if appropriate, in the presence of a solvent, into compounds of theformula (VIII), according to the reaction scheme below (Scheme 1):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl,C₁-C₄-alkoxycarbonyl and benzyloxycarbonyl, M= for example MgCl, MgBr,MgI, Li, R⁹═C₁-C₄-alkyl or C₃-C₆-cycloalkyl, W, X, and R² are as definedfor formula (I) in claim 1; (b) the reaction of alcohols of the formula(VIII) with an oxidizing agent in the presence of a solvent, to giveketones of the formula (IX), according to the reaction scheme below(Scheme 2):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl andC₁-C₄-alkoxycarbonyl, R⁹═C₁-C₄-alkyl or C₃-C₆-cycloalkyl, W, X, and R²are as defined for formula (I) in claim 1; (c) the conversion of ketonesof the formula (IX) in the presence of a base or an acid and, ifappropriate, a solvent, into compounds of the formula (IVb), accordingto the reaction scheme below (Scheme 3):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl andC₁-C₄-alkoxycarbonyl, L²=—CR⁹═CR⁹—, W, X, L³, R², R³ and R⁹ are asdefined for formula (I) in claim 1; (d) the conversion of aldehydes ofthe formula (VII) in the presence of a base or an acid and, ifappropriate, a solvent, into compounds of the formula (IVb), accordingto the reaction scheme below (Scheme 4):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl andC₁-C₄-alkoxycarbonyl, L²=—CR⁹═CR⁹—, W, X, L³, R², R³ and R⁹ are asdefined for formula (I) in claim 1; (e) the conversion of aldehydes ofthe formula (VII) in the presence of a base and, if appropriate, asolvent, into alkynes of the formula (X) according to the reactionscheme below (Scheme 5):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl andC₁-C₄-alkoxycarbonyl, W, X and R² are as defined for formula (I) inclaim 1; (f) the reaction of alkynes of the formula (X) with anR³-L³-halide in an optionally catalyzed C—C coupling reaction in thepresence of a base and, if appropriate, a solvent, to give compounds ofthe formula (IVc), according to the reaction scheme below (Scheme 6):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl andC₁-C₄-alkoxycarbonyl, Hal=Cl, Br or I, L²=—C≡C—, W, X, L³, R² and R³ areas defined for formula (I) in claim 1; (g) the reaction of alkynes ofthe formula (X) with a trialkylsilyl chloride (R¹⁰R¹¹R¹²)SiCl ortrialkylsilyl triflate (R¹⁰R¹¹R¹²)SiOSO₂CF₃ or other known silylatingagents in the presence of a base and, if appropriate, a solvent, to givecompounds of the formula (XI), according to the reaction scheme below(Scheme 7):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl andC₁-C₄-alkoxycarbonyl, R¹⁰, R¹¹ and R¹²═C₁-C₄ alkyl or phenyl, W, X andR² are as defined for formula (I) in claim 1; (h) the reaction ofalkynes of the formula (XI) with a compound R³-L³-Hal, if appropriate inthe presence of a catalyst, in the presence of a base and, ifappropriate, a solvent, to give compounds of the formula (IVc),according to the reaction scheme below (Scheme 8):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl andC₁-C₄-alkoxycarbonyl, Hal=Cl, Br or I, R²=hydrogen, C₁-C₂-alkyl orC₁-C₂-haloalkyl, L²=—C≡C—, R¹⁰, R¹¹ and R¹²═C₁-C₄-alkyl or phenyl, W, X,L³ and R³ are as defined for formula (I) in claim 1; (i) the reaction ofthioamides of the formula (V) with compounds of the formula (VIa) or(VIb) in the presence of a base and, if appropriate, in the presence ofa solvent, to give compounds of the formula (IVa) or (IVb), according tothe reaction scheme below (Scheme 9):

where PG=unsubstituted or substituted phenylmethyl (where thesubstituents independently of one another are selected from the groupconsisting of methyl, methoxy, nitro, dioxolano), acetyl,C₁-C₄-alkoxycarbonyl and benzyloxycarbonyl, Hal=Cl, Br or I,L²=—C(R⁸)₂—C(R⁸)₂— for compounds of the formula (IVa) and (VIa),L²=—CR⁹═CR⁹— for compounds of the formula (IVb) and (VIb), W, X, L³, R²,R³, R⁸ and R⁹ are as defined for formula (I) in claim 1; (j) theconversion of compounds of the formula (IVb) or (IVc) in the presence ofhydrogen, a catalyst and, if appropriate, a solvent, into compounds ofthe formula (IVa), according to the reaction scheme below, (Scheme 10):

where PG=acetyl or C₁-C₄-alkoxycarbonyl, L²=—C(R⁸)₂—C(R⁸)₂— forcompounds of the formula (IVa), L²=—CR⁹═CR⁹— for compounds of theformula (IVb), L²=—C≡C— for compounds of the formula (IVc), W, X, L³,R², R³, R⁸ and R⁹ are as defined for formula (I) in claim 1; (k) theconversion of compounds of the formula (IV), if appropriate in thepresence of a solvent and, if appropriate, in the presence of an acidor, if appropriate, in the presence of a base or, if appropriate, in thepresence of a source of hydrogen, into compounds of the formula (II),according to the reaction scheme below (Scheme 11):

where PG=acetyl, C₁-C₄-alkoxycarbonyl or benzyloxycarbonyl, W, X, L²,L³, R², and R³ are as defined for formula (I) in claim 1; (l) theconversion of compounds of the formula (IIa′) in the presence of ahalogenating agent, if appropriate in the presence of an acid and asolvent, into compounds of the formula (IIa), according to the reactionscheme below (Scheme 12):

where L²=—C(R⁸)₂—C(R⁸)₂—, R²═I, Br or Cl for compounds of the formula(IIa), R²=hydrogen for compounds of the formula (IIa′), W, X, L³, R³ andR⁸ are as defined for formula (I) in claim 1; (m) the reaction ofcompounds of the formula (III) with compounds of the formula (II), ifappropriate in the presence of a coupling agent, a base and a solvent,to give compounds of the formula (I), according to the reaction schemebelow (Scheme 13):

where B═OH, chlorine, bromine or iodine, Y=oxygen, A, W, X, L¹, L², L³,R², and R³ are as defined for formula (I) in claim 1; (n) the conversionof compounds of the formula (I) in the presence of a sulphurizing agentand, if appropriate, in the presence of a solvent, into compounds of theformula (I), according to the reaction scheme below (Scheme 14):

where A, W, X, L¹, L², L³, R², and R³ are as defined for formula (I) inclaim
 1. 10. Process for preparing the compounds of the formula (I),comprising at least one of steps (o) to (u) below: (o) the conversion ofaldehydes of the formula (XII) in the presence of a base and, ifappropriate, a solvent, into alkynes of the formula (XIII), according tothe reaction scheme below (Scheme 17):

where A, W, X, Y, L¹ and R² are as defined for formula (I) in claim 1;(p) the reaction of alkynes of the formula (XIII) with a trialkylsilylchloride (R¹⁰R¹¹R¹²)SiCl or trialkylsilyl triflate (R¹⁰R¹¹R¹²)SiOSO₂CF₃or other known silylating agents in the presence of a base and, ifappropriate, a solvent, to give compounds of the formula (XIV),according to the reaction scheme below (Scheme 18):

where R¹⁰, R¹¹ and R¹²═C₁-C₄ alkyl or phenyl, A, W, X, Y, L¹ and R² areas defined for formula (I) in claim 1; (q) the reaction of alkynes ofthe formula (XIII) with an R³-L³-halide in an optionally catalyzed C—Ccoupling reaction in the presence of a base and, if appropriate, asolvent, to give compounds of the formula (Ic), according to thereaction scheme below (Scheme 19):

where Hal=Cl, Br or I, L²=—C≡C—, A, W, X, Y, L¹ L³, R² and R³ are asdefined for formula (I) in claim 1; (r) the reaction of alkynes of theformula (XIV) with a compound R³-L³-Hal, if appropriate in the presenceof a catalyst, in the presence of a base and, if appropriate, a solvent,to give compounds of the formula (Ic), according to the reaction schemebelow (Scheme 20):

where Hal=Cl, Br or I, L²=—C≡C—, R¹⁰, R¹¹ and R¹² ═C₁-C₄-alkyl orphenyl, A, W, X, Y, L¹ L³, R² and R³ are as defined for formula (I) inclaim 1; (s) the conversion of aldehydes of the formula (XII) in thepresence of a base or an acid and, if appropriate, a solvent, intocompounds of the formula (Ib), according to the reaction scheme below(Scheme 21):

where L²=—CR⁹═CR⁹—, A, W, X, Y, L¹ L³, R², R³ and R⁹ are as defined forformula (I) in claim 1; (t) the conversion of compounds of the formula(Ic) in the presence of hydrogen, a catalyst and, if appropriate, asolvent, into compounds of the formula (Ib), according to the reactionscheme below (Scheme 22):

where L²=—CR⁹═CR⁹— for compounds of the formula (Ib), L²=—C≡C— forcompounds of the formula (Ic), A, W, X, Y, L¹ L³, R², R³ and R⁹ are asdefined for formula (I) in claim 1; (u) the conversion of compounds ofthe formula (Ib) or (Ic) in the presence of hydrogen, a catalyst and, ifappropriate, a solvent, into compounds of the formula (Ia), according tothe reaction scheme below (Scheme 23):

where L²=—C(R⁸)₂—C(R⁸)₂— for compounds of the formula (Ia), L²=—CR⁹═CR⁹—for compounds of the formula (Ib), L²=—C≡C— for compounds of the formula(Ic), A, W, X, Y, L¹ L³, R², R³, R⁸ and R⁹ are as defined for formula(I) in claim 1.